研究者総覧

棚瀬 知明 (タナセ トモアキ)

  • 研究院自然科学系化学領域 教授
メールアドレス:
tanasecc.nara-wu.ac.jp
Last Updated :2021/06/02

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学位

  • 工学博士, 東京大学

研究キーワード

  • 錯体化学 有機金属化学 生物無機化学 遷移金属クラスター 分子性金属鎖 多座ホスフィン 

研究分野

  • ナノテク・材料, 機能物性化学, 金属クラスター
  • ナノテク・材料, 無機・錯体化学, 配位化学
  • ナノテク・材料, 有機合成化学, 有機金属化学
  • ナノテク・材料, 生体化学, 生物無機化学

経歴

  • 2000年04月 奈良女子大学理学部化学科・教授
  • 1996年09月 奈良女子大学理学部化学科・助教授
  • 1996年04月 東邦大学理学部化学科・助教授
  • 1993年 - 1995年 マサチューセッツ工科大学化学科(米国)・客員教授
  • 1989年 - 1993年 理化学研究所分子構造解析室・嘱託研究員
  • 1991年10月 東邦大学理学部化学科・講師
  • 1988年04月 東邦大学理学部化学科・助手

学歴

  • - 1988年03月 東京大学 工学系研究科 合成化学専攻
  • - 1983年03月 東京大学 工学部 工業化学科

委員歴

  • 2014年10月 英国王立化学協会 フェロー society

    学協会

  • 2016年10月 - 2018年09月 錯体化学会 副会長 society

    学協会

論文

  • Tetranuclear zigzag Ag4 and Ag2Pt2 complexes supported by rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (rac-dpmppm)

    Tomoaki Tanase; Risa Otaki; Kanako Nakamae; Yasuyuki Ura; Takayuki Nakajima

    © 2020 Elsevier B.V. Reaction of AgOTf with a tetraphosphine, rac-bis[(diphenylphosphinomethyl) phenylphosphino]methane (rac-dpmppm), afforded [Ag4(rac-dpmppm)2](TfO)4 (3) which consists of zigzag-arrayed tetranuclear silver(I) ions supported by syn-arrangement of two enantiomeric (RR/SS) dpmppm ligands. Complex 3 readily reacted with XylNC (Xyl = 2,6-dimethylphenyl) to give [Ag4(rac-dpmppm)2(XylNC)2](TfO)4 (4), where two terminal isocyanides attach to the outer Ag sites. Complex 3 has been shown a good precursor for Pt-Ag-Ag-Pt mixed metal array as incubation of 3 with trans-[Pt(C[tbnd]CPh)2(PPh3)2] yielded [Ag2Pt2(C[tbnd]CPh)4(rac-dpmppm)2](TfO)2 (5). Two trans-Pt(C[tbnd]CPh)2 units are incorporated into the terminal positions in a site-selective fashion and the Pt-Ag-Ag-Pt tetranuclear core also adopts a zigzag array supported by syn-arrangement of two rac-dpmppm ligands. The d8 and d10 closed-shell mixed metal centers of 5 exhibited an intense photoluminescence at 534 nm, mainly from an unsymmetric triplet state generated by charge transfer transitions from ligand (acetylide π) to metal centers (Ag2 and PtAg s/pσ), 3LMCT, and to ligands (acetylide π* and dpmppm), 3LLCT. The present results provide fundamental and useful information to construct multinuclear closed-shell metal alignments by utilizing polyphosphine ligands., Elsevier, 2020年10月15日, J. Organomet. Chem., 925, 121488, 国際誌, 国際共著していない, doi;scopus;scopus_citedby

    研究論文(学術雑誌)

  • Multinuclear Copper Hydride Complexes Supported by Polyphosphine Ligands

    Takayuki Nakajima; Kanako Nakamae; Yasuyuki Ura; Tomoaki Tanase

    © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Copper hydride compounds have attracted interest in diverse fields as base metallic material in place of rare and noble metals, which have widely been utilized in hydrogenation catalysts, hydrogen storage, and electrochemical materials. Since the first report on the synthesis of copper hydride complex [Cu6H6(PPh3)6] in 1971, copper hydride reagents have been utilized in a variety of organic transformation. While well-characterized copper hydride complexes have been long limited to a few examples, recently several research groups have reported the synthesis of phosphine-stabilized copper hydride complexes with various metal-frameworks and unique reactivity. Here we review recent progress on the synthesis and structures of copper hydride complexes supported by phosphine ligands, including di-, tri-, and tetraphosphines, and also describe their reactivity with CO2., Wiley-VCH (European Chemical Society Publishing), 2020年06月23日, Eur. J. Inorg. Chem., 2020 (23), 2211 - 2226, 国際誌, 国際共著していない, doi;scopus;scopus_citedby

    研究論文(学術雑誌)

  • Transition Metal Clusters Constrained by Linear Tetradentate Phosphine Ligands

    Takayuki Nakajima; Tomoaki Tanase

    The Chemical Society of Japan, 2020年04月05日, Chem. Lett., 49 (4), 386 - 394, 国際誌, doi;url;scopus;scopus_citedby

    研究論文(学術雑誌)

  • Facially Dispersed Polyhydride Cu9 and Cu16 Clusters Comprising Apex‐Truncated Supertetrahedral and Square‐Face‐Capped Cuboctahedral Copper Frameworks

    Kanako Nakamae; Takayuki Nakajima; Yasuyuki Ura; Yasutaka Kitagawa; Tomoaki Tanase

    Wiley-VCH (European Chemical Society Publishing), 2020年02月03日, Angew. Chem. Int. Ed., 59 (6), 2262 - 2267, 国際誌, doi;url;url;url

    研究論文(学術雑誌)

  • Dinuclear Copper Complexes Triply Bridged by a Tetraphosphane, rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2

    Tomoaki Tanase; Risa Otaki; Ayumi Okue; Kanako Nakamae; Takayuki Nakajima

    2019年10月09日, Eur. J. Inorg. Chem., 2019 (37), 3993 - 4005, 国際誌, 国際共著していない, doi;url

    研究論文(学術雑誌)

  • Tetra-, hexa- and octanuclear copper hydride complexes supported by tridentate phosphine ligands

    Takayuki Nakajima; Kanako Nakamae; Rika Hatano; Kaho Imai; Masafumi Harada; Yasuyuki Ura; Tomoaki Tanase

    Tetra-, hexa-, and octanuclear copper hydride complexes were synthesized by using a triphosphine, Ph2PCH2P(Ph)CH2PPh2 (dpmp), and were characterized by X-ray crystallographic analyses and theoretical calculations.

    , 2019年07月18日, Dalton Trans., 48 (32), 12050 - 12059, 国際誌, 国際共著していない, doi;url

    研究論文(学術雑誌)

  • N-Acyclic carbene complexes supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an asymmetric pincer ligand

    Tomoaki Tanase; Mari Urabe; Natsumi Mori; Satoko Hatada; Sayo Noda; Hiroe Takenaka; Kanako Nakamae; Takayuki Nakajima

    Elsevier BV, 2019年01月, J. Organomet. Chem., 879, 47 - 59, 国際誌, 国際共著していない, doi

    研究論文(学術雑誌)

  • A decanuclear Pt complex comprised of an unbridged Pt4 chain capped by two Pt3 A-frame units supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2

    Tomoaki Tanase; Mari Urabe; Hiroe Takenaka; Kanako Nakamae; Takayuki Nakajima

    Elsevier BV, 2019年03月, J. Organomet. Chem., 883, 41 - 46, 国際誌, 国際共著していない, doi

    研究論文(学術雑誌)

  • Synthesis and characterization of iridium hydride complexes with meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an unsymmetric pincer ligand

    Tomoaki Tanase; Natsumi Mori; Kanako Nakamae; Takayuki Nakajima

    2019年06月, J. Organomet. Chem., 888, 54 - 64, 国際誌, 国際共著していない, doi

    研究論文(学術雑誌)

  • Alloyed Tetranuclear Metal Chains of Pd4−nPtn (n = 0–3) Scaffolded by a New Linear Tetraphosphine Containing a PNP Bridge

    Tomoaki Tanase; Miho Tanaka; Mami Hamada; Yuka Morita; Kanako Nakamae; Yasuyuki Ura; Takayuki Nakajima

    Wiley-VCH (European Chemical Society Publishing), 2019年06月21日, Chemistry – A European Journal, 25 (35), 8219 - 8224, 国際誌, doi;url;url

    研究論文(学術雑誌)

  • Synergistic Cu2 Catalysts for Formic Acid Dehydrogenation

    Takayuki Nakajima; Yoshia Kamiryo; Masayo Kishimoto; Kaho Imai; Kanako Nakamae; Yasuyuki Ura; Tomoaki Tanase

    2019年06月05日, J. Am. Chem. Soc., 141 (22), 8732 - 8736, 国際誌, 国際共著していない, doi;url

    研究論文(学術雑誌)

  • Tri- and Tetranuclear Copper Hydride Complexes Supported by Tetradentate Phosphine Ligands

    T. Nakajima; Y. Kamiryo; K. Hachiken; K. Nakamae; Y. Ura; T. Tanase

    2018年08月, Inorg. Chem., 57, 11005-11018, doi

  • Synthesis and Reactivity of Thiolate-Bridged (NiMI)-M-II Heterodinuclear Complexes (M = Rh, Ir) with an S-Bidentate NiP2S2 Metalloligand

    Bunsho Kure; Mikie Sano; Natsuki Watanabe; Takayuki Nakajima; Tomoaki Tanase

    The mononuclear complex [Ni(meppp)] {H(2)meppp = meso-1,3-bis[(2-mercaptoethyl)(phenyl)phosphino]propane} was used as an S-bidentate NiP2S2 metalloligand to prepare a series of (NiMI)-M-II complexes with various neutral ligands, namely, [Ni(mu-meppp)ML2]PF6 [M = Rh, L = 1/2cod (1a; cod = 1,5-cycloocatadiene), CO (1b), XylNC (1c; Xyl = 2,6-dimethylphenyl), P(OPh)(3) (1d); M = Ir, L = 1/2cod (2a), CO (2b), XylNC (2c)]. The reactivities of 1 and 2 toward methyl iodide and tertiary hydrosilanes were examined. Complexes 1c, 2a, and 2b reacted with MeI to afford the oxidative addition products [Ni(mu-meppp)M(L)(2)(Me)(I)]PF6 [M = Rh, L = XylNC (3c); M = Ir, L = 1/2cod (4a)] and [Ni(mu-meppp)Ir(CO)(Me)(I)(2)] (5). In the reactions with hydrosilanes, only 2c exhibited an interesting reactivity to afford the Ni-II(mu-H)Ir-III silyl complexes [Ni(mu-meppp)(mu-H)Ir(XylNC)(2)(Si)]PF6 [Si = SiEt3 (6a), SiMe2Ph (6b), SiMePh2 (6c), SiPh3 (6d)]. The reaction proceeded via the intermediate isomers [Ni(meppp)(mu-H)Ir(XylNC)(2)(Si)]PF6 (7); intermediate 7d (Si = SiPh3) was characterized and has an Ni-II(mu-H)Ir-III silyl structure with the hydrido ligand nesting in the reverse side of the Ni(mu-S)(2)Ir pocket to that of 6d. These results demonstrated that the reactivities of the bis(thiolate)-bridged (NiMI)-M-II heterodinuclear complexes can be tuned by changing the metal ions and ancillary ligands. In addition, the S-bidentate NiP2S2 metalloligand [Ni(meppp)] plays an important role in the stabilization of the bridging hydrido ligand in both pockets of the Ni-II(mu-H)Ir-III core owing to the flexibility of the hinged Ni(mu-SR)(2)Ir structure., 2017年09月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (35), 4097 - 4109, doi;web_of_science

    研究論文(学術雑誌)

  • A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO2

    Kanako Nakamae; Miho Tanaka; Bunsho Kure; Takayuki Nakajima; Yasuyuki Ura; Tomoaki Tanase

    A copper hydride cluster [Cu-8(m-H)(6)(mu-dppm) (5)](PF6)(2) (dppm= bis(diphenylphosphino) methane) was prepared from reaction of [CuH(PPh3)](6) with dppm in the presence of [Cu(CH3CN)(4)] PF6 and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans-bicapped octahedral Cu-8 framework. The Cu8H6 complex showed facile reactivity with CO2 (1 atm, RT) to afford a tricopper complex, [Cu-3(m-H)(m-O2CH)(m-dppm)(3)] PF6, which could be developed to unprecedented hydrosilylation of CO2 catalyzed by multinuclear CuH species under mild conditions., 2017年07月, CHEMISTRY-A EUROPEAN JOURNAL, 23 (40), 9457 - 9461, doi;web_of_science

    研究論文(学術雑誌)

  • Linear Triplatinum Tetrahydride Complex Supported by Triphosphine Ligands, [Pt-3(mu-H)(2)(H)(2)(mu-dpmp)(2)](BF4)(2) {dpmp = bis(diphenylphosphinomethyl)phenylphosphine}

    Tomoaki Tanase; Kana Yamamoto; Rika Hatano; Kanako Nakamae; Bunsho Kure; Yasuyuki Ura; Takayuki Nakajima

    By treating [Pt6(mu-H)(H)(2)(mu-dpmp)(4)]BH4 [4, dpmp = bis(diphenylphosphinomethyl) phenylphosphine] with an excess amount of HBF4 in N, N-dimethylformamide (DMF), a triplatinum tetrahydride complex, [Pt-3(mu-H)(2)(H)(2)(mu-dpmp)(2)](BF4)(2) (5), was obtained in 51 % yield and was characterized by IR, UV/Vis, H-1 NMR, and P-31{H-1} NMR spectroscopy in addition to ESI mass spectrometry, X-ray crystallography, and DFT calculations. Complex 5 is composed of linear trinuclear platinum centers supported by two dpmp ligands, {Pt-3(mu-dpmp) 2}(6+), which accommodate two terminal and two bridging hydrides in a HPtHPtHPtH zigzag structure. The hydride positions were deter-mined by DFT optimization with B3LYP/GD3BJ functionals. Variable- temperature H-1{P-31} NMR spectroscopy in [D7]DMF revealed that the bridging hydrides exhibit fluxional behavior and migrate along the Pt3 chain by switching the bridging site, whereas the terminal hydrides are not exchanged with the bridging ones. The present results suggest that the divalent linear triplatinum unit of {Pt-3(mu-dpmp)(2)}(2+) (Pt-3(II)), which is a building block to construct [Pt-6(mu-H)(H)(2)(mu-dpmp)(4)](+) (4, Pt-3(II)-Pt-3(II)), formally acts as a four-electron source to result in [Pt-3(mu-H)(2)(H)(2)(mu-dpmp)(2)](2+) (5, Pt-3(VI)) through protonation., 2017年03月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (11), 1422 - 1426, doi;web_of_science

    研究論文(学術雑誌)

  • Chiral Self-Recognition between Stereogenic Tetrapalladium Units Affording Pd-8 Chains Supported by Homochiral Tetraphosphines

    Tomoaki Tanase; Konomi Morita; Risa Otaki; Kana Yamamoto; Yukino Kaneko; Kanako Nakamae; Bunsho Kure; Takayuki Nakajima

    By using a chiral tetraphosphine, rac-bis[(diphenylphosphinomethyl)phenylphosphino]methane (rac-dpmppm), linear octapalladium chains were synthesized as discrete molecules of [Pd-8(mu-rac-dpmppm)(4)L-2](BF4)(4) (L=CH3CN, dmf, XylNC), [Pd-8(mu-rac-dpmppm)(4)](BF4)(4), and [Pd-8(mu-rac-dpmppm)(4)(Cl)(2)](BF4)(2), which are stable in the solution states and characterized by spectroscopic and crystallographic methods to reveal the octapalladium chains supported by homochiral four tetraphosphines. Variable-temperature NMR studies for a 1:1 mixture of [Pd-8(mu-rac-dpmppm)(4)(dmf)(2)](BF4)(4) and [Pd-8(mu-meso-dpmppm)(4)(dmf)(2)](BF4)(4) in [D-7]DMF revealed that the Pd-8 chains were dissociated at higher temperature (T approximate to 140 degrees C) into the Pd-4 units of {Pd-4(mu-rac-dpmppm)(2)}(2+) and {Pd-4(mu-meso-dpmppm) 2}(2+), and they were thermodynamically self-aligned to restore the Pd-8 chains at lower temperature (T < 60 degrees C), through perfect chiral self-recognition between the stereogenic tetrapalladium units., 2017年01月, CHEMISTRY-A EUROPEAN JOURNAL, 23 (3), 524 - 528, doi;web_of_science

    研究論文(学術雑誌)

  • Planar PtPd3 Complexes Stabilized by Three Bridging Silylene Ligands

    Tanabe, Makoto; Yumoto, Ryouhei; Yamada, Tetsuyuki; Fukuta, Tomoko; Hoshino, Tsuyoshi; Osakada, Kohtaro; Tanase, Tomoaki

    A heterobimetallic PtPd3 complex supported by three bridging diphenylsilylene ligands, [Pt{Pd(dmpe)}(3)(mu(3)-SiPh2)(3)] (1, dmpe = 1,2-bis(dimethylphosphino) ethane), has been synthesized from mononuclear Pd and Pt complexes. The hexagonal core composed of Pt, Pd, and Si atoms is slightly larger than that of the tetrapalladium complex, [Pd{Pd(dmpe)}(3)(mu(3)-SiPh2)(3)] (2). Reaction of PhSiH3 with complex 1 in the presence and absence of Ph2SiH2 results in the formation of a tetranuclear complex with silyl and hydride ligands at the Pt center, [PtH(SiPh2H){Pd(dmpe)}(3)(mu 3SiHPh)(3)] (3), and an octanuclear complex, [{Pt{Pd(dmpe)}(3)(mu(3)-SiHPh)(3)}(2)(kappa(-2)-dmpe)] (5), respectively. Both M-Si (M = Pt, Pd) bond lengths and the Si-29 NMR chemical shifts of 1 and 2 are located between those of mononuclear late transitionmetal complexes with a silylene ligand and complexes with donor-stabilized silylene ligands. CuI and AgI adducts of 1 and 2, formulated as [M(mu-M'I){Pd(dmpe)}(3)(mu(3)-SiPh2)(3)] (M = Pt, Pd; M' = Cu, Ag), undergo elimination of CuI (AgI) and regenerate the tetrametallic complexes upon heating or addition of a chelating diphosphine. Elimination of AgI from 2-AgI occurs more rapidly than elimination of CuI from 2-CuI, as determined from the results of kinetics experiments., 2017年01月, CHEMISTRY-A EUROPEAN JOURNAL, 23 (6), 1386 - 1392, doi;web_of_science

    研究論文(学術雑誌)

  • Homo- and Heterodinuclear Rh and Ir Complexes Supported by SNn Mixed -Donor Ligands (n=2-4): Stereochemistry and Coordination -Site -Exchange Reactions of Cp*M (M Rh, Ir) Units

    Takayuki Nakajima; Yuki Kawasaki; Bunsho Kure; Tomoaki Tanase

    A series of SNn mixed-donor ligands [n = 2: H2NC2H4SCH2-2-pyridyl (2-NSpY) (1a), H2NC2H4SCH2-4-pyridyl (4-NSpy) (1b), n = 3: 2-pyridylCH(2)NHC(2)H(4)SCH(2)-2-pyridyl (2-pyNSpy) (2), n = 4: (2-pyridylCH(2))(2)NC2H4SCH2-2-pyridyl (2-py2NSPY) (3)] was utilized to support homo- and heterodinuclear complexes including Cp*MIII units (M = Rh, Ir; Cp* = pentamethylcyclopentadienyl). Reactions of [Cp*MCI2](2) with 2-pyNSpy (2), 2-py(2)NSpy (3), and 4-NSpy (1b) afforded homodinulear complexes, [(Cp*MC1)(2-pyNSpy)(Cp*MCI)(1)(PF6)(2) [M = Rh (5a), Ir (5b)], [(Cp*M)(2-py2NSpy)(Cp*MCW(PF6)3 [M = Rh (6a), Ir (6b)], [(Cp*MCI)(4-NSpy)(Cp*MC12)1C1 [M = Rh (8a), Ir (8b)L Heterodinuclear complexes [(Cp*MCI)(4-NSpy)(Cp*M,Cl-2)[Cl [M, M' = Rh, Ir (8c), Ir, Rh (8d)] were prepared using mononuclear complexes [(Cp*MC1)(4-NSpy)1C1 [I\A = Rh (7a), Ir (7b)] reacted with [Cp*MCI2](2) (M = Ir, Rh), respectively. Complexes 5-8 were characterized by X-ray crystallography to determine the configurations around the M, M', 5, and N centers. The solid-state structures of 6 are retained in acetonitrile solution whereas four diastereomers are generated in the case of 5 due to low stereo selectivity around the coordinated amine nitrogen atom, in contrast to the sulfur atom. Heterodinuclear complexes 8c,d are unstable in solution at 55 degrees C, readily affording mixtures of 8a-d via intra- and intermolecular coordination-site-exchange reactions of Cp*M fragments between the SN moiety and the py site. In order to evaluate the selectivity of Cp*M fragments for the SN and py coordination sites, several competitive reactions of [Cp*MCl2](2) (M = Rh, Ir) with H2NC2H4SCH2C6H5 (NSph) (4) and/or 4-methylpyridine (4-Mepy) were carried out to demonstrate predominant formation of iridium complexes 9b and 10b among [(Cp*MCl)(NSph)]Cl EM = Rh (9a), Ir (9b)] and [(Cp*MCl)(4-Mepy)Kl [M = Rh (10a), Ir (10b)]. These reactions indicated higher affinity of the COI- fragment to both the NS and py sites relative to the rhodium analogue., 2016年10月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (28), 4701 - 4710, doi;web_of_science

    研究論文(学術雑誌)

  • Synthesis and structure of trihydride hexaplatinum complex supported by triphosphine ligands, [Pt-6(mu-H)(H)(2)(mu-dpmp)(4)]BH4 (dpmp = bis(diphenylphosphino-methyl)phenylphosphine)

    Tomoaki Tanase; Kana Yamamoto; Kanako Nakamae; Bunsho Kure; Takayuki Nakajima

    From a reaction of [Pt-3(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (1a) with NaBH4 and [Pt(dba)(2)] in N,N-dimethyl formamide (DMF), a trihydride hexaplatinum complex, [Pt-6(mu-H)(H)(2)(mu-dpmp)(4)]BH4 center dot DMF (4*center dot DMF), was isolated as dark green crystals in 47% yield, and was characterized by IR, UVevis, H-1 and P-31{H-1} NMR, and ESI mass spectral analyses, X-ray crystallography, and DFT calculations. Complex 4* is stable in DMF and DMSO solutions, and contains two terminal and one bridging hydrides observed at -5.92 ppm ((1)J(PtH) = 980 Hz) and -4.47 ppm ((1)J(PtH) = 591 Hz) in the H-1 NMR spectrum(DMSO-d(6)). The X-ray diffraction analysis revealed the linear hexaplatinum structure supported by four dpmp ligands, wherein two {Pt-3(H)(m-dpmp)(2)}(+) units are connected by the bridging hydride resulting in a long Pt/Pt separation (3.3075(6) angstrom) between the central two Pt atoms. Other Pt-Pt distances range from 2.7243(7) to 2.7499(6) angstrom, indicating the presence of PtePt bonds within the {Pt-3(mu-dpmp)(2)} units. On the basis of the crystal structure, the hydride positions were optimized by DFT calculations to show a bent bridging hydride (av. Pt-H = 1.65 angstrom, Pt-H-Pt = 160.0 degrees) as well as linear terminal ones (av. Pt-H = 1.68 angstrom, av. Pt-Pt-H = 179.4 degrees). The present study provides useful information in expanding molecular metallic chains by utilizing {H-Pt-3-H-Pt-3-H}(+) building blocks. (C) 2016 Elsevier B.V. All rights reserved., 2016年07月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 814, 35 - 41, doi;web_of_science

    研究論文(学術雑誌)

  • Systematic Synthesis of Di-, Tri-, and Tetranuclear Homo- and Heterometal Complexes Using a Mononuclear Copper Synthon with a Tetradentate Amino Alcohol Ligand

    Takayuki Nakajima; Chisako Yamashiro; Megumi Taya; Bunsho Kure; Tomoaki Tanase

    The reaction of Cu(NO3)(2)center dot 3H(2)O with an N2O2 tetradentate amino alcohol, N,N-dibenzyl-N',N'-bis(2-hydroxyethyl)ethylenediamine (H2L), afforded the mononuclear copper complex [Cu(H2L)(NO3)](NO3) (1), which has been used to construct a series of di-, tri-, and tetranuclear homo-and heterometallic complexes. Complex 1 dimerized in the presence of NEt3 to form the Cu-2 complex [Cu-2(HL)(2)](NO3)(2) (2) by the deprotonation of one of the two hydroxy groups in the H2L ligand. The reaction of 1 with Cu(OCOH)(2) in the presence of NEt3 afforded the Cu-3 complex [Cu-3(HL)(2)(OCOH)(2)](NO3)(2) (5). The metalloligand {Cu(HL)}(+) derived from 1 reacted with M(OAc)(2) (M = Cu, Co, Zn, Ni) in the absence of NEt3 to form the asymmetric CuM dinuclear complexes [CuM(HL)(OAc)(NO3)(2)] [M = Cu (3a), Co (3b), Zn (3c), Ni (3d)], whereas in the presence of NEt3 a unit of M(OAc) was captured by two metalloligands to give the bent CuMCu trinuclear complexes [Cu2M(HL)(2)(OAc)(2)(NO3)](NO3) [M = Cu (4a), Co (4b), Mn (4c)], which were further transformed into the linear CuMCu trinuclear complexes [Cu-3(HL)(2){(PhO)(2)PO2}(2)](NO3)(2) (7a) and [Cu2M(HL)(2){(PhO)(2)PO2}(2)(MeOH)(2)](NO3)(2) [M = Co (7b), Mn (7c)] with the aid of diphenyl phosphate bridging ligands. When (PhO) PO2(OH) was used as an auxiliary bridging ligand in the reaction of 1 with M(OAc)(2) and NEt3, the Cu2M2 tetranuclear complexes [Cu2M2(HL)(2){(PhO) PO3}(2)(NO3)(2)] [M = Co (8a), Zn (8b)] were synthesized. These results demonstrate that the mononuclear copper synthon with the N2O2 tetradentate amino alcohol ligand {Cu(H2L)}(2+) generates the quite useful metalloligand {Cu(HL)}(+) by the deprotonation of a hydroxy group, and subsequent reactions lead to the construction of a series of homo-and heterometal complexes containing Cu-2, CuM (M = Cu, Co, Zn, Ni), bent-CuMCu (M = Cu, Co, Mn), linear-CuMCu (M = Cu, Co, Mn), and Cu2M2 (M = Co, Mn) cores in a systematic and selective manner., 2016年06月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (17), 2764 - 2773, doi;web_of_science

    研究論文(学術雑誌)

  • Oxidative addition of an aromatic ortho C-H bond of tetraphosphine to asymmetric diiridium(I) centres

    Takayuki Nakajima; Sayo Noda; Miyuki Sakamoto; Aya Matsui; Kanako Nakamae; Bunsho Kure; Yasuyuki Ura; Tomoaki Tanase

    Reactions of a tetraphosphine, meso-bis{[(diphenylphosphinomethyl) phenyl] phosphino} propane (dpmppp), with [IrCl(cod)](2) and CO (1 atm) or isocyanide (RNC) in the presence of NH4PF6 at 80-100 degrees C in dichloromethane/acetonitrile/acetone and/or methanol mixed solvents afforded asymmetric diiridium(II) complexes, [Ir-2(H)(Cl)(mu-(dpmppp-H)-kappa(PC)-C-4)(CO)(3)]PF6 (1) and [Ir-2(H)(mu-(dpmppp-H)-kappa(PC)-C-4)(RNC)(4))]-(PF6)(2) (R = 2,6-xylyl (2), 2,4,6-mesityl (3); dpmppp-H = {PPh(o-C6H4)CH2P(Ph)(CH2)(3)P(Ph) CH2PPh2}(-)). A similar reaction with (BuNC)-Bu-t resulted in the formation of a mononuclear Ir-III complex of [Ir(H)(dpmppp-kappa P-3)((BuNC)-Bu-t)(2)](PF6)(2) (4). Complexes 1-3 were characterized by ESI mass spectrometry, H-1 and P-31 NMR spectroscopy and X-ray diffraction analyses. They were found to consist of cis/trans-P, P asymmetric (IrII-IrII) bonded dinuclear structures derived from oxidative addition of an ortho C-H bond of dpmppp (Ir-Ir = 2.8044(2) angstrom (1), 2.8569(2) angstrom (2), and 2.8524(5) angstrom (3)), resulting in a [IrPCCIr] intermetallic cyclometal-bridge and a terminal hydride. DFT calculations indicated the presence of Ir-Ir, Ir-H, and Ir-C-ortho covalent bonds. Initial stages of the reactions with CO and XylNC at room temperature were investigated by P-31{H-1} NMR spectroscopy and found to contain a symmetrical Ir-I dinuclear unit with dpmppp that was readily transformed into 1 and 2 upon heating. The Ir-2(I) intermediate with XylNC, [Ir-2(XylNC)(4)(mu-dpmppp)] (PF6)(2) (6), was isolated and characterized by X-ray crystallography and DFT calculations as an electron-deficient 32e(-)Ir(2)(I) species involving a IrI. IrI dative bond (2.7989(5) angstrom). The reaction pathways from 6 to 2 were investigated by DFT calculations. The present study suggested that a novel oxidative addition of an ortho C-H bond proceeded on the cis/trans-P, P asymmetric diiridium(I) scaffold supported by the tetraphosphine, dpmppp, which was assumed to be facilitated by dimetal cooperation with switching Ir -> Ir dative interactions., 2016年, DALTON TRANSACTIONS, 45 (11), 4747 - 4761, doi;web_of_science

    研究論文(学術雑誌)

  • Electron-rich linear triplatinum complexes stabilized by a spinning tetraphosphine, tris(diphenylphosphinomethyl)phosphine

    Tomoaki Tanase; Kanako Koike; Miho Uegaki; Satoko Hatada; Kanako Nakamae; Bunsho Kure; Yasuyuki Ura; Takayuki Nakajima

    Linear triplatinum complexes with 48e(-), [Pt3(mu-tdpmp)(2)(RNC)(2)](PF6)(2) (R = 2,6-xylyl (3), Bu-t (4)), were synthesized by using a branched tetraphosphine, tris(diphenylphosphinomethyl) phosphine (tdpmp), and characterized by crystallographic and spectroscopic analyses to show their novel dynamic behaviour in the solution state, in which the linear Pt3 unit was stabilized by two spinning tetraphosphine ligands., 2016年, DALTON TRANSACTIONS, 45 (17), 7209 - 7214, doi;web_of_science

    研究論文(学術雑誌)

  • Gold and Silver Chains Supported by Linear Hexaphosphine Ligands

    Tomoaki Tanase; Mio Chikanishi; Konomi Morita; Kanako Nakamae; Bunsho Kure; Takayuki Nakajima

    A new linear hexaphosphine, rac-cis,cis,trans-bis{[(diphenylphosphinomethyl)phenylphosphinomethyl]-phenylphosphino}methane (P-6), was synthesized and isolated as a pure isomer, confirmed by transforming to the corresponding phosphine sulfide. The methylene-bridged linear hexaphosphine readily organized flexible gold(I) and silver(I) hexanuclear chains, [M-6(mu-P-6)(2)]X-6 (X-6=(OTf)(6), M=Au (1), Ag (2); X-6=Cl-2(PF6)(4), M=Au (3)). The hexaphosphine also supported a tetrasilver(I) complex [Ag-4(mu-P-6)(2)](OTf)(4) (4), which was readily transformed by treatment with AgOTf into 3, revealing a drastic alternation of the two P-6 arrangement. The hexagold(I) chains exhibited a considerably red-shifted absorption (similar to 410 nm) and emission (540-580 nm) to (1)[5d(sigma*)-> 6p(sigma)] and from (3)[5d(sigma*)-> 6p(sigma)] excited states of the metal centers, respectively. The new linear hexaphosphine could be a useful tool to construct linear metal clusters as subnano building blocks., 2015年12月, CHEMISTRY-AN ASIAN JOURNAL, 10 (12), 2618 - 2622, doi;web_of_science

    研究論文(学術雑誌)

  • Synthesis and structures of dinuclear Rh-III and Ir-III complexes supported by a tetraphosphine, meso- or rac-bis {[(diphenylphosphinomethyl)phenyl]phosphino]}methane

    Tomoaki Tanase; Akiko Yoshii; Risa Otaki; Kanako Nakamae; Yumina Mikita; Bunsho Kure; Takayuki Nakajima

    Reactions of [Cp*MCl2](2) with meso-or rac-dpmppm in the presence of NH4PF6 afforded mixtures of stereoisomers formulated as [(Cp*MCl)(2)(meso- or rac-dpmppm)](PF6)(2), from which the major isomers, rac-M-2-[(Cp*MCl)(2)(meso-dpmppm)](PF6)(2) (M = Rh (1a), Ir (1b)) and rac-M-2-[(Cp*MCl)(2)(rac-dpmppm)](PF6)(2) (M = Rh (2a), Ir (2b)), were isolated and characterized by IR, UV-vis, ESI mass, and H-1 and P-31{H-1} NMR spectroscopy and X-ray crystallography, where dpmppm is bis{[(diphenylphosphino-methyl) phenyl] phosphino}methane and Cp* is eta(5)-pentamethylcyclopentadienyl. The isomeric tetra-phosphine incorporates two {Cp*MCl} fragments with four-membered chelation through a pair of outer and inner phosphine units, and fixes them ca. 6.9 angstrom apart from each other. The configurations around the metal centers in 2 were determined to avoid repulsive interaction between the phenyl group on the inner P atom and the M-bound chloride anion, while those in 1 would be determined by minimizing not only the Ph/Cl repulsion but also repulsion between the two metal fragments. In the dichloromethane solutions, the major isomers 1 and 2 were not converted to any other minor isomers even at high temperature, but in dmf and dmso, only 1a was readily transformed into the minor isomer, meso-M-2-[(Cp*RhCl)(2)(meso-dpmppm)](PF6)(2). Cyclic voltammograms of 1a, b and 2a, b demonstrated two irreversible 2e reduction waves corresponding to (MMIII)-M-III -> (MMIII)-M-I -> (MMI)-M-I, in which the mixed-valence states with meso-dpmppm could be stabilized to a larger extent than with rac-dpmppm. Complex 1a heated in acetonitrile with AgOTf/NH4OTf afforded a Rh2Ag2 mixed-metal complex, [(Cp*Rh(CH3CN))(2)Ag-2(OTf)(2)(meso-dpmppm)(2)](OTf)(4) (5). (C) 2015 Elsevier B.V. All rights reserved., 2015年11月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 797, 37 - 45, doi;web_of_science

    研究論文(学術雑誌)

  • Stepwise Expansion of Pd Chains from Binuclear Palladium(I) Complexes Supported by Tetraphosphine Ligands

    Tomoaki Tanase; Satoko Hatada; Sayo Noda; Hiroe Takenaka; Kanako Nakamae; Bunsho Kure; Takayuki Nakajima

    Reaction of [Pd-2(XyINC)(6)]X-2 (X = PF6, BF4) with a linear tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm), afforded binuclear Pd-I complexes, [Pd-2(mu-dpmppm)(2)]X-2 ([2]X-2), through an asymmetric dipallachum complex, [Pd-2(mu-dpmppm)(XylNC)(3)](2+) ([1](2+)). Complex [2](2+) readily reacted with [Pd-0(dba)(2)] (2 equiv) and an excess of isocyanide, RNC (R = 2,6-xylyl (Xyl), tert-butyl (Bu-t), to generate an equilibrium mixture of [Pd-4(mu-dpmppm),(RNC)(2)](2+) ([3'](2+)) + RNC reversible arrow [Pd-4(mu-dpmppm)(2) (RNC)(3)](2+) ([3](2+)), from which [Pd-4(mu-dpmppm)2(XylNC)(3)](2+) ([3a](2+)) and [Pd-4(mu-dpmppm)(2) ((BUNC)-B-t)(2)](2+) ([3b'](2+)) were isolated. Variable-temperature UV-vis and P-31{H-1} and H-1 NMR spectroscopic studies on the equilibrium mixtures demonstrated that the tetrapalladium complexes are quite fluxional in the solution state: the symmetric Pd-4 complex [3b'](2+) predominantly existed at higher temperatures (>0 degrees C), and the equilibrium shifted to the asymmetric Pd-4 complex [3b'](2+) at a low temperature (similar to-30 degrees C). The binding constants were determined by UV-vis titration at 20 degrees C and revealed that XylNC is of higher affinity to the Pd-4 core than (BuNC)-Bu-t. In addition, both isocyanides exhibited higher affinity to the electron deficient [Pd-4(mu-dpmppmF(2))(2)(RNC)(2)](2+) ([3F'](2+)) than to [Pd-4(mu-dpmppm)(2)(RNC)(2)](2+) ([3'](2+)) (dpmppmF(2) = meso-bisadi(3,5-difluorophenyl)phosphinomethyl}phenylphosphino]methane). When [2] X-2 was treated with [Pd-0(dba)(2)] (2 equiv) in the absence of RNC in acetonitrile, linearly ordered octapalladium chains, [Pd-8(mu-dpmppm)(4)(CH3CN)(2)]X-4 ([4]X-4: X = PF6, BF4), were generated through a coupling of two {Pd-4(mu-dpmppm)(2)}(2+) fragments. Complex [2](2+) was also proven to be a good precursor for Pd2M2 mixed-metal complexes, yielding [Pd2Cl(Cp*MCl) (Cp*MCl2)(mu-dpmppm)(2)](2+) (M = Rh ([5](2+)), Ir ([6](2+)), and [Au2Pd2Cl2(dpmppm-H)(2)](2+) ([7])(2+) by treatment with [Cp*MCl2](2) and [AuCl(PPh3)], respectively. Complex [7]2+ contains an unprecedented PC(sp(3))P pincer ligand with a PCPCPCP backbone, dpmppm H of deprotonated dpmppm. The present results demonstrated that the binuclear Pd-I complex [2](2+) was a quite useful starting material to extend the palladium chains and to construct Pd-involved heteromultinuclear systems., 2015年09月, INORGANIC CHEMISTRY, 54 (17), 8298 - 8309, doi;web_of_science

    研究論文(学術雑誌)

  • Self-Alignment of Low-Valent Octanuclear Palladium Atoms

    Kanako Nakamae; Yukie Takemura; Bunsho Kure; Takayuki Nakajima; Yasutaka Kitagawa; Tomoaki Tanase

    A linear tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) was used to synthesize linear octapalladium-extended metal atom chains as discrete molecules of [Pd-8(mu-dpmppm)(4)](BF4)(4) (1) and [Pd-8(mu-dpmppm)(4)L-2](BF4)(4) (L = 2,6-xylyl isocyanide (XylNC; 2), acetonitrile (3), and N, N-dimethylformamide (dmf; 4)), which are stable in the solution states and show interesting temperature-dependent photochemical properties in the near IR region. Variable temperature NMR studies demonstrated that at higher temperature T approximate to 140 degrees C the Pd-8 chains were dissociated into Pd-4 fragments, which were thermodynamically self-aligned to restore the Pd-8 chains at lower temperature T < 60 degrees C. The coldspray ionization mass spectra suggested a possibility for further aggregation of the linear tetrapalladium units., 2015年01月, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 54 (3), 1016 - 1021, doi;web_of_science

    研究論文(学術雑誌)

  • Facile Insertion of Carbon Dioxide into Cu-2(mu-H) Dinuclear Units Supported by Tetraphosphine Ligands

    Kanako Nakamae; Bunsho Kure; Takayuki Nakajima; Yasuyuki Ura; Tomoaki Tanase

    Reactions of meso-bis[(diphenylphosphinomethyl) phenylphosphino] methane (dpmppm) with Cu-I species in the presence of NaBH4 afforded di- and tetranuclear copper hydride complexes, [Cu-2(mu-H)(mu-dpmppm)(2)]X (1) and [Cu-4(mu-H)(2)(mu(4)-H)(mu-dpmppm)(2)]X (2) (X = BF4, PF6). Complex 1 undergoes facile insertion of CO2 (1 atm) at room temperature, leading to a formate-bridged dicopper complex [Cu-2(mu-HCOO)(dpmppm)(2)]X (3). The experimental and DFT theoretical studies clearly demonstrate that CO2 insertion into the Cu-2(mu-H) unit occurred with the flexible dicopper platform. Complex 2 also undergoes CO2 insertion to give a formate-bridged complex, [Cu-4(mu-HCOO)(3)(dpmppm)(2)]X, during which the square Cu-4 framework opened up to a linear tetranuclear chain., 2014年11月, CHEMISTRY-AN ASIAN JOURNAL, 9 (11), 3106 - 3110, doi;web_of_science

    研究論文(学術雑誌)

  • Tetranuclear Nickel and Cobalt Complexes with an Incomplete Double-Cubane Structure-Homo- and Heterometallic Complexes and Their 1D Coordination Polymers

    Takayuki Nakajima; Keiko Seto; Andreas Scheurer; Bunsho Kure; Takashi Kajiwara; Tomoaki Tanase; Masahiro Mikuriya; Hiroshi Sakiyama

    The reactions of M(OAc)(2 center dot)4H(2)O (M = Ni, Co) with three unsymmetrical amine-did l ligands RN(CH2CH2OH)-(CH2CH2CH2OH) (H2Ln: n =1 , R = benzyl, n = 2, R = 4-methylenzyl]; n = 3, R = 2-naphthalenylmethyl) in the presence of NEt3 or pyridine in MeOH or BnOH gave the tetranuclear complexes [M-4(HLn)(2)(OAc)(6)(MeOH)(2)] {M = Ni, n = 1 (la), 2 (lb), 3 (1c) M = Co, n = 1 (4a), 2 (4b), 3 (4c)} and [M-4(HLn)(2)-(OAc)(6)(BnOH)(2)] {M = Ni, n = 1 (2a), 2 (2b), 3 (2c); M = Co, n = 1 (5a), 2 (5b), 3 (5c)}. When p-xylene-alpha,alpha'-diol was used instead of monoalcohols, the tetranuclear (M4O6) units were linked by p-xylene-alpha,alpha'-diol to form the 1D coordination polymers [M-4(HLn)(2)(OAc)(6)(p-HOH2C6H4CH2OH)](m) {M = Ni, n = 1 (3a), 2 (3b); M = Co, n = 1 (6a), 2 (6b)). The structures of 1-6 were determined by X-ray crystallography and consist of centrosymmetrical tetranuclear (M4O6)) face-shared defective double-cubane cores supported by two monodeprotonated (HLn-) ligands. The mixed-metal letranuclear complexes [Ni2.2Co1.8(HL1)(2)(OAc)(6)(MeOH)(2)] (7) and [Mn1.7Ni2.3(HL1)(2)(OAc)(5)(OMe)(2)] (8) were also synthesized by using e.quimolar amounts of Ni2+ and M2+ (M = Co, Mn) ions. X-ray crystallographic and :fluorescent analyses.revealed that 7 is isomorphous with 1a and 4a and contains.nonstoichiometric amounts of disordered Ni2+ and Co2+ ions in an average ratio of 2.2:1.8 with different occupancies for the two crystallographically independent metal centers. In contrast, 8 consists of a C-2-symmetrical face-shared defective doublecubane ((M3MnO6)-Mn-II-O-III) core with a Ni/Mn ratio of 2.3:1.7, the amounts of Ni2+ and Mn2+ ions vary depending on the metal sites, and one of the C-2 axial positions is exclusively occupied by Nin ions. Detailed magnetostru.ctural analyses on the nickel (1a, 2a, 3a) mid cobalt (4a) complexes with appropriate spin-Hamiltoulau. models showed that both iferro- and antiferromagnetic spin exchange interactions were involved within the tetranuclear units, and their extent depends on the combination of the metal ions and -the ligand systems in a delicate fashion., 2014年10月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (29), 5021 - 5033, doi;web_of_science

    研究論文(学術雑誌)

  • Synthesis and structures of Pd2M2 (M = Cu, Au) and Pd2M (M = Cu, Ag) mixed-metal complexes supported by NPPN tetradentate ligands

    Takayuki Nakajima; Minori Tsuji; Naoko Hamada; Yuki Fukushima; Bunsho Kure; Tomoaki Tanase

    Reactions of [PdCl(Me)(cod)] with two NPPN mixed-donor tetradentate ligands, meso-2-pyridylCH(2)(Ph) P(CH2)(2)P(Ph)CH2-2-pyridyl (meso-picppe) and rac-2-pyridylCH(2)(Ph)P(CH2)(4)P(Ph)CH2-2-pyridyl (rac-picppb), afforded dinuclear palladium complexes [(PdCl(Me))(2)(meso-picppe)] (1) and [(PdCl(Me))(2)(rac-picppb)] (2), which were further converted with 2,6-xylyl isocyanide (XylNC) to [(PdCl(C(=NXyl) Me))(2)(meso-picppe)] (3) and {(PdCl(C(=NXyl)Me))(2)(rac-picppb)] (4) through insertion of XylNC into the Pd-Me bonds. Complexes 3 and 4 possess two imidoyl moieties which are of potential donors and readily capture d(10) group 11 metal ions depending on their stereostructures of the NPPN ligands. Reactions of 3 with CuCl or AuCl(tht) afforded Pd2M2 mixed-metal tetranuclear complexes [(PdCl(C(=NXyl) Me)(MCl))(2)(meso-picppe)] (M = Cu (5a), Au (5b)), where each imidoyl moiety captures a MCI fragment in a C-i symmetrical fashion. Similar reactions of 4 with [Cu(MeCN)(4)]BF4 or AgBF4 resulted in Pd2M trinuclear complexes [(PdCl(C(=NXyl)Me)(2)M(rac-picppb)]BF4 (M = Cu (6a), Ag (6b)), in which two imino groups chelate a M-I ion with a pseudo C-2 symmetrical structure. (C) 2014 Elsevier B.V. All rights reserved., 2014年10月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 768, 61 - 67, doi;web_of_science

    研究論文(学術雑誌)

  • Systematic Heterodinuclear Complexes with MM’(??meppp) Centers That Tune Property of a Nesting Hydride, M = Ni, Pd, Pt; M’ = Rh, Ir; H2meppp = meso-1,3-Bis[(mercaptoethyl)phenylphosphino]-propane

    Bunsho Kure; Mikie Sano; Takayuki Nakajima; Tomoaki Tanase

    Mononuclear complexes with a P2S2 ligand, [M(meppp) (M = Ni (1a), Pd (1b), Pt (1c); H(2)meppp = meso-1,3-bis[(mercaptoethyl)phenylphosphino]propane), were treated with [M'Cp*Cl-2](2) or [M'Cp*(NO3)(2)] (Cp* = eta(5)-pentamethylcyclopentadienyl) to afford a series of bisthiolate-bridged (MM)-M-II'(III) heterodinuclear complexes, [M(mu-meppp)-M'Cp*X]X' (M = Ni, Pd, Pt; M' = Rh, It; X = Cl, NO3; X' = Cl, PF6, NO3). The nitrate complexes [M(mu-meppp)-M'Cp*(NO3)]NO3 (M' = Rh ([4a-c]NO3), Ir ([5a-c]NO3); M = Ni (a), Pd (b), Pt (c)) further reacted with sodium formate in water or methanol to be transformed into bisthiolate- and hydride-bridged complexes, [M(mu-meppp)(mu-H)M'Cp*]NO3 (M' = Rh ([6a-c]NO3), Ir ([8a-c]NO3); M = Ni (a), Pd (b), Pt (c)). Complexes [6a]NO3 (M = Ni, M' = Rh) and [8a]NO3 (M = Ni, M' = Ir) were characterized by X-ray analyses to reveal that a hydride is stabilized in a semibridging mode on the heterometal centers. In the (PdRhIII)-Rh-II ([6b]NO3) and (PtRhIII)-Rh-II ([6c]NO3) complexes, the hydrides were extremely unstable and were likely to undergo an unusual metal-to-Cp* ring hydrogen transfer, resulting in eta(4)-C5Me5H (MRhI)-Rh-II complexes, [M(mu-meppp)Rh(eta(4)-C5Me5H)]NO3 (M = Pd ([7b]NO3), Pt ([7c]NO3)). The property of the hydride was drastically switched by varying the anchoring metal ions of the M' site (Rh, Ir); that of [6a]NO3 (M' = Rh) is not protic and decomposes in water below pH 4, while those of [8a-c]NO3 (M' = Ir) are protic, subject to H+/D+ exchange reactions, and stable below pH 4. [6a]NO3 reacted with phenylacetylene to give [Ni(mu-meppp)RhCp*(C CPh)]NO3 ([10a]NO3), which is in contrast with the inertness of the (NiIrIII)-Ir-II hydride complex [8a]NO3. The reaction is assumed to involve an alkenyl complex, [Ni(mu-meppp)RhCp*(CH=CHPh)]NO3 (9a), formed through an insertion of phenylacetylene into the metal-hydride bond. Analogous (MRhIII)-Rh-II alkynyl complexes, [M(mu-meppp)RhCp*(C CPh)]NO3 (M = Pd ([10b]NO3), Pt ([10c]NO3)), were synthesized by treating [4b,c]NO3 with phenylacetylene in basic media, and the structural differences among [10a-c]NO3 were discussed. These results interestingly demonstrated that the structures, properties, and reactivities of the nesting hydride on the {MM'(mu-meppp)} cores were tuned by varying metal ions of the M and M' sites., 2014年08月, ORGANOMETALLICS, 33 (15), 3950 - 3965, doi;web_of_science

    研究論文(学術雑誌)

  • One-dimensional Anisotropic Metal-Organic Module Containing a Pt-6 Chain Terminated with Redox Active Ferrocenyl Units

    Tomoaki Tanase; Chie Yamamoto; Bunsho Kure; Takayuki Nakajima

    A 1D anisotropic hexaplatinum chain with redox-active terminal ligands, [Pt-6(mu-H)(mu-dpmp)(4)(FcDipNC)(2)](PF6)(3) (7) (dpmp: bis(diphenylphosphinomethyl)phenylphosphine, FcDipNC: 2,6-dlisopropyl-4-(ferrocenylethynylene)phenyl isocyanide), was synthesized, its structure and electrochemical behavior were elucidated in comparison with those of [Pt-6(mu-H)(mu-dpmp)(4)(DipNC)(2)](PF6)(3) (6) (DipNC: 2,6-diisopropylphenyl isocyanide), and the module was found to undergo two stepwise two-electron oxidations., 2014年06月, CHEMISTRY LETTERS, 43 (6), 913 - 915, doi;web_of_science

    研究論文(学術雑誌)

  • Electron-Deficient Pt2M2Pt2 Hexanuclear Metal Strings (M = Pt, Pd) Supported by Triphosphine Ligands

    Eri Goto; Rowshan Ara Begum; Chiaki Ueno; Aya Hosokawa; Chie Yamamoto; Kanako Nakamae; Bunsho Kure; Takayuki Nakajima; Takashi Kajiwara; Tomoaki Tanase

    Electron-deficient Pt2M2Pt2 hexanuclear clusters, [Pt4M2(mu-dpmp)(4)(XylNC)(2)](PF6)(4) (M = Pt (7), Pd (8); dpmp = bis((diphenylphosphino)methyl)phenylphosphine), were synthesized by oxidation of hydride-bridged hexanuclear clusters [Pt4M2(mu-H)(mu-dpmp)(4)(XylNC)(2)](PF6)(3) (M = Pt (2), Pd (3)) and were revealed to involve a linearly ordered Pt2M2Pt2 array joined by delocalized bonding interactions with 84 cluster valence electrons, which are discussed on the basis of DFT calculations. The central MM distances of 7 and 8 are significantly reduced upon the apparent loss of a hydride unit from the MHM central part of 2 and 3, indicating that the bonding electrons in the adjacent MPt bonds migrate into the central MM bond to result in a dynamic structural change during two-electron oxidation of the hexanuclear metal strings. A similar Pt-6 complex terminated by two iodide anions, [Pt6I2(mu-dpmp)(4)](PF6)(2) (9), was synthesized from [Pt-6(mu-H)I-2(mu-dpmp)(4)](PF6) (5) by treatment with [Cp2Fe][PF6]. Complexes 7 and 8 were readily reacted with the neutral two-electron donors XylNC, CO, and phosphines to afford the trinuclear complexes [Pt2M(mu-dpmp)(2)(XylNC)L](PF6)(2) (M = Pt, L = XylNC (la), CO (10), PPh3 (11); M = Pd, L = XylNC (1b)) through cleavage of the electron-deficient central M-M bond. 'When complex 7 was reacted with the diphosphines (PP) trans-Ph2PCH=CHPPh2 (dppen) and Ph2P(CH2)(2)PPh2 (dppe), the diphosphine was inserted into the central M-M bond to afford [(XylNC)Pt-3(mu-dpmp)(2)(PP)Pt-3(mu-dpmp)(2)(XylNC)](PF6)(4) (12), which was transformed by treatment with another 1 equiv of diphosphine into the asymmetric trinuclear complexes [Pt-3(mu-dpmp)(2)(XylNC)(PP)](PF6)(2) (13). A further ligand exchange reaction of 13a (PP = trans-dppen) provided the diphosphine-terminated symmetrical Pt3 complex [Pt-3(mu-dpmp)(2)(L)(2)](PF6)(2) (L = trans-dppen (14a)). Complexes 7 and 8 were also reacted with [AuCl(PPh3)] to yield the Pt2MAu heterotetranuclear complexes [Pt2MAuCl(mu-dpmp)(2)(PPh3)(XylNC)RPF6)(2) (M = Pt (15), Pd (16)), in which the Pt2M trinuclear fragment is inserted into the Au-Cl bond in a 1,1-fashion on the central M atoms of the Pt2M2Pt2 string., 2014年04月, ORGANOMETALLICS, 33 (8), 1893 - 1904, doi;web_of_science

    研究論文(学術雑誌)

  • Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso- or rac-Bis[(diphenylphosphinomethyl)phenylphosphino]methane

    Tomoaki Tanase; Risa Otaki; Tomoko Nishida; Hiroe Takenaka; Yukie Takemura; Bunsho Kure; Takayuki Nakajima; Yasutaka Kitagawa; Taro Tsubomura

    A series of tetragold(I) complexes supported by tetraphosphine ligands, meso- and rac-bis[(diphenylphosphinomethyl)phenylphosphino] methane (meso- and rac-dpmppm) were synthesized and characterized to show that the tetranuclear Au-I alignment varies depending on syn- and anti-arrangements of the two dpmppm ligands with respect to the metal chain. The structures of syn-[Au-4(meso-dpmppm)(2)X]X-3' (X=Cl; X'=Cl (4a), PF6 (4b), BF4 (4c)) and syn-[Au-4(meso-dpmppm)(2)]X-4 (X=PF6 (4d), BF4 (4e), TfO (4 f); TfO=triflate) involved a bent tetragold(I) core with a counter anion X incorporated into the bent pocket. Complexes anti-[Au-4(meso-dpmppm)(2)]X-4 (X=PF6 (5d), BF4 (5e), TfO (5 f)) contain a linearly ordered Au-4 string and complexes syn-[Au-4(rac-dpmppm)(2)X-2]X-2' (X=Cl, X'=Cl (6a), PF6 (6b), BF4 (6c)) and syn-[Au-4(rac-dpmppm)(2)]X-4 (X=PF6 (6d), BF4 (6e), TfO (6 f)) consist of a zigzag tetragold(I) chain supported by the two syn-arranged rac-dpmppm ligands. Complexes 4d-f, 5d-f, and 6d-f with non-coordinative large anions are strongly luminescent in the solid state (lambda(max)=475-515 nm, Phi=0.67-0.85) and in acetonitrile (lambda(max)=491-520 nm, Phi=0.33-0.97); the emission was assigned to phosphorescence from 3[d(sigma*sigma*sigma*)p(sigma sigma sigma)] excited state of the Au-4 centers on the basis of DFT calculations as well as the long lifetime (a few mu s). The emission energy is predominantly determined by the HOMO and LUMO characters of the Au-4 centers, which depend on the bent (4), linear (5), and zigzag (6) alignments. The strong emissions in acetonitrile were quenched by chloride anions through simultaneous dynamic and static quenching processes, in which static binding of chloride ions to the Au-4 excited species should be the most effective. The present study demonstrates that the structures of linear tetranuclear gold(I) chains can be modified by utilizing the stereoisomeric tetraphosphines, meso- and rac-dpmppm, which may lead to fine tuning of the strongly luminescent properties intrinsic to the Au-4(I) cluster centers., 2014年02月, CHEMISTRY-A EUROPEAN JOURNAL, 20 (6), 1577 - 1596, doi;web_of_science

    研究論文(学術雑誌)

  • Configurational Isomerization of Dinuclear Iridium and Rhodium Complexes with a Series of NPPN Ligands, 2-PyCH2(Ph)P(CH2)nP(Ph)CH2-2-Py (Py = Pyridyl, n=2-4)

    Takayuki Nakajima; Yuki Fukushima; Minori Tsuji; Naoko Hamada; Bunsho Kure; Tomoaki Tanase

    New heterodonor NPPN tetradentate ligands, 2-PyCH2(Ph)P-(CH2)(n) P(Ph)CH2-2-Py (meso- and rac-L-n; n = 2-4, Py = pyridyl), were prepared and reacted with [Cp*MCl2](2) (M = Ir, Rh; Cp* is pentamethylcyclopentadienyl) in the presence of NH4BF4 to afford a series of dinuclear complexes [(Cp*MCl)(2)(meso-L-n)](BF4)(2) (M = Ir, n = 2 (2a), 3 (3a), 4 (4a); M = Rh, n = 2 (2c), 3 (3c), 4 (4c)) and [(Cp*MCl)(2)(rac-L-n)](BF4)(2) (M = Ir, n = 2 (2b), 3 (3b), 4 (4b); M = Rh, n =, 2 (2d), 3 (3d), 4 (4d)), which were characterized by IR, H-1 and (31)p{H-1} NMR, and ESI mass spectroscopic techniques and X-ray crystallography. The configurations around the two metal centers were controlled by the configuration of the coordinated P atoms so as to avoid repulsive interaction between the phenyl group on P and the chloride ligand, resulting in the formation of stereospecific isomers; a mesa configuration of the metal centers is induced from meso-L-n (abbreviated as meso-P-2/meso-M-2), and in contrast, a rac configuration is induced from rac-L" (rac-P-2/rac-M-2). Furthermore, inversion of metal centers for the Ir-2 complexes occurred in DMSO at higher temperatures (60-100 degrees C), generating equilibrium mixtures of minor diastereomers (meso-P-2/rac-M-2 or rac-P-2/meso-M-2) in low ratios together with the major isomers (meso-P-2/meso-M-2 or rac-P-2/rac-M-2). The equilibrium constants, K = [minor isomer]/[major isomer], varied appreciably depending on the lengths of the methylene chains as well as configurations of the NPPN ligands; the overall propensity for the K values was observed to be L-2 < L-3 <L-4 and meso-L-n < rac-L-n, while rac-L-3, rac-L-4, and meso-L-4 showed almost identical equilibrium constants, presumably resulting from no steric influence between the two metal centers., 2013年12月, ORGANOMETALLICS, 32 (24), 7470 - 7477, doi;web_of_science

    研究論文(学術雑誌)

  • Systematic Conversion of Single Walled Carbon Nanotubes into n-type Thermoelectric Materials by Molecular Dopants

    Yoshiyuki Nonoguchi; Kenji Ohashi; Rui Kanazawa; Koji Ashiba; Kenji Hata; Tetsuya Nakagawa; Chihaya Adachi; Tomoaki Tanase; Tsuyoshi Kawai

    Thermoelectrics is a challenging issue for modern and future energy conversion and recovery technology. Carbon nanotubes are promising active thermoelectic materials owing to their narrow bandgap energy and high charge carrier mobility, and they can be integrated into flexible thermoelectrics that can recover any waste heat. We here report air-stable n-type single walled carbon nanotubes with a variety of weak electron donors in the range of HOMO level between ca. -4.4 eV and ca. -5.6 eV, in which partial uphill electron injection from the dopant to the conduction band of single walled carbon nanotubes is dominant. We display flexible films of the doped single walled carbon nanotubes possessing significantly large thermoelectric effect, which is applicable to flexible ambient thermoelectric, 2013年11月, SCIENTIFIC REPORTS, 3, 3:3344, doi;web_of_science

    研究論文(学術雑誌)

  • Reversible dioxygen binding on asymmetric dinuclear rhodium centres

    Takayuki Nakajima; Miyuki Sakamoto; Sachi Kurai; Bunsho Kure; Tomoaki Tanase

    Electron-deficient dinuclear rhodium complexes [Rh< inf> 2< /inf> Cl < inf> 2< /inf> (μ-dpmppp)(RNC)] (1), with the linear tetraphosphine ligand dpmppp, showed reversible binding of molecular oxygen to form asymmetric dirhodium η< sup> 2< /sup> -peroxo complexes [Rh< inf> 2< /inf> Cl < inf> 2< /inf> (O< inf> 2< /inf> )(μ-dpmppp)(RNC)] (2) stabilized by a Rh→Rh dative bond. © The Royal Society of Chemistry 2013., 2013年06月11日, Chemical Communications, 49 (46), 5250 - 5252, doi

    研究論文(学術雑誌)

  • Synthesis and structure of a dinuclear (NiIrIII)-Ir-II hydride complex supported by a N3S2 bridging ligand: Comparison of property and reactivity of dinuclear Ni-II(mu-H)M-III units (M = Rh, Ir) in aqueous media

    Bunsho Kure; Takayuki Nakajima; Tomoaki Tanase

    A water-soluble dinuclear (NiIrIII)-Ir-II complex with a bridging hydride, [Cp* Ir(mu-H)Ni(TsTACN(C2H4S)(2))]NO3 (TsTACN(C2H4SH)(2) = 1,4-bis(2-mercaptoethyl)-7-tosyl-1,4,7-triazacyclononane, Cp* = eta(5)-penta-methyl-cyclopentadienyl, [2b]NO3), was synthesized by reacting a dinuclear (NiIrIII)-Ir-II complex [Cp*Ir(NO3)Ni(TsTACN(C2H4S)(2))]NO3 ([1b]NO3) with HCOONa in water. The structure of [2b] NO3 was unequivocally determined by an X-ray analysis to allow comparing its structure, property, and reactivity in aqueous media to those of the corresponding rhodium counterpart, [Cp*Rh(mu-H)Ni(TsTACN(C2H4S)(2))]NO3 ([2a] NO3). The Ni center dot center dot center dot Ir distance (av. 2.721 angstrom) is slightly longer than the Ni/ Rh separation (av. 2.691 angstrom). The hydrido ligand of Ni-II(mu-H) Ir-III complex ([2b]NO3) bears protic character and is stable in water above pH 2, which is contrasted to the fact that the hydrido ligand of NiII(mu-H) Rh-III([2a]NO3) has no protic character and is stable in water only above pH 6. The difference of the hydride stability in water may lead to a difference of their reductivity, in which [2b]NO3 barely reduced benzaldehyde to benzyl alcohol only in acidic media (pH 3) although the rhodium analog [2a]NO3 did promote the reaction in neutral water. Theoretical calculations with DFT methods on model compounds [Cp*M(mu-H) Ni(HTACN(CH2CH2S)(2))]+(M = Rh ([3a](+)), Ir ([3b](+))) revealed that the hydrido ligand of the Ni(mu-H) Ir has less bridging character with a stronger interaction with the Ir-III center than that with the Rh-III center in the Ni(mu-H) Rh unit. (C) 2013 Elsevier B.V. All rights reserved., 2013年06月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 733, 28 - 35, doi;web_of_science

    研究論文(学術雑誌)

  • Flexible, linear, tetranuclear palladium complexes supported by tetraphosphine ligands with electron-withdrawing groups

    Tomoaki Tanase; Satoko Hatada; Ayaka Mochizuki; Kanako Nakamae; Bunsho Kure; Takayuki Nakajima

    A linearly ordered tetraphosphine containing electron-withdrawing substituent groups on the outer phosphorus atoms, meso-bis[{di(3,5-difluorophenyl)phosphinomethyl}phenylphosphino]methane (dpmppmF(2)), was prepared and reacted with [Pd-2(RNC)(6)](PF6)(2) and Pd(dba)(2) to afford tetranuclear palladium complexes, [Pd-4(mu-dpmppmF(2))(2)(RNC)(3)](PF6)(2) (R = 2,6-xylyl (Xyl) (1), 2,4,6-mesityl (2), 2,6-diisopropylphenyl (3) and tert-butyl (4)), which involve an asymmetric {(RNC)Pd-4(CNR)(2)}(2+) core supported by two dpmppmF(2) ligands in anti-arrangement. Each terminal of the Pd4 chain was capped by terminal isocyanide and a semi-bridging RNC is introduced into one terminal Pd site. Mechanistic investigation suggested that the dipalladium(I) complex, [Pd-2(mu-dpmppmF(2))(2)(RNC)(2)](PF6)(2) (R = Xyl (6)), was a key intermediate to trap Pd-0 species by the uncoordinated outer phosphine pendants with electron-withdrawing groups. Variable-temperature UV-vis and P-31{H-1}, H-1 NMR spectroscopic studies demonstrated that the tetrapalladium complexes are quite fluxional in the solution state at high temperature (>20 degrees C) relating to a symmetric structure of [Pd4(mu-dpmppmF2) 2(RNC) 2](PF6) 2, and the asymmetric solid state structures are retained even in the solution at low temperature (<-60 degrees C). Theoretical calculations with DFT methods on the asymmetric (R = Xyl (1)) and symmetric (R = Xyl (1')) structures suggested that contribution of Pd-0 -> Pd-I-Pd-0-Pd-I with 60 cluster valence electrons (CVEs) would be dominant in 1, while the symmetric structure of 1' can be recognized as Pd-I-Pd-0-Pd-0-Pd-I with 58 CVEs. The new tetraphosphine dpmppmF2 was proven very effective in organizing dynamically flexible tetrapalladium chains., 2013年, DALTON TRANSACTIONS, 42 (45), 15941 - 15952, doi;web_of_science

    研究論文(学術雑誌)

  • Hydride-Bridged Pt2M2Pt2 Hexanuclear Metal Strings (M = Pt, Pd) Derived from Reductive Coupling of Pt2M Building Blocks Supported by Triphosphine Ligands

    Eri Goto; Rowshan Ara Begum; Aya Hosokawa; Chie Yamamoto; Bunsho Kure; Takayuki Nakajima; Tomoaki Tanase

    Linear Pt2M2Pt2 hexanuclear clusters [Pt4M2(mu-H)(mu-dpmp)(4)(XylNC)(2)](PF6)(3) (M = Pt (2a), Pd (3a); dpmp = bis(diphenylphosphinomethyl)phenylphosphine) were synthesized by site-selective reductive coupling of trinuclear building blocks, [Pt2M(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (M = Pt (1a), Pd (1b)), and were revealed as the first example of low-oxidation-state metal strings bridged by a hydride with M-H-M linear structure. The characteristic intense absorption bands around 583 nm (2a) and 674 nm (3a) were assigned to the HOMO-LUMO transition on the basis of a net three-center/two-electron (3c/2e) bonding interaction within the central M-2(mu-H) part. The terminal ligands of 2a were replaced by H-, I-, and CO to afford [Pt-6(mu-H)(H)(2)(mu-dpmp)(4)](+) (4), [Pt-6(mu-H)I-2(mu-dpmp)(4)](PF6) (5), and [Pt-6(mu-H)(mu-dpmp)(4)(CO)(2)](PF6)(3) (6). The electronic structures of these hexaplatinum cores, {Pt-6(mu-H)(mu-dpmp)(4)}(3+), are varied depending on the sigma-donating ability of axial ligands; the characteristic HOMO-LUMO transition bands interestingly red-shifted in the order of CO < XylNC < I- < H- which was in agreement with calculated HOMO-LUMO gaps derived from DFT optimizations of 2a, 4, 5, and 6. The nature of the axial ligands influences the redox activities of the hexanuclear complexes; 2a, 3a, and 5 were proven to be redox-active by the cyclic voltammograms and underwent two-electron oxidation by potentiostatic electrolysis to afford [Pt4M2(mu-dpmp)(4)(XylNC)(2)](PF6)(4) (M = Pt (7a), Pd (8a)). The present results are important in developing bottom-up synthetic methodology to create nanostructured metal strings by utilizing fine-tunable metallic building blocks., 2012年12月, ORGANOMETALLICS, 31 (24), 8482 - 8497, doi;web_of_science

    研究論文(学術雑誌)

  • Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of Ni-II, Co-II, and Cu-II Ions Supported by Unsymmetrical Aminoalcohol Ligands

    Takayuki Nakajima; Keiko Seto; Fumihiro Horikawa; Isao Shimizu; Andreas Scheurer; Bunsho Kure; Takashi Kajiwara; Tomoaki Tanase; Masahiro Mikuriya

    Reactions of M(OAc)(2)center dot 4H(2)O (M = Ni, Co) with 3-[benzyl(2-hydroxyethypamino]-1-propanol (H2L) in the presence of pyridine or triethylamine afforded novel homometallic icosanuclear wheel-shaped complexes [M20L4(HL)(4)(OAc)(28)] (M = Ni (1), Co (2)), which consist of a central M-12(II) single-stranded, nearly planar loop with four peripheral [M-2(HL)(OAc)(2)] fragments attached in an S-4 symmetrical fashion. The complexes can alternatively be recognized as saddle-shaped wheel structures, in which four tetranuclear units of [M4L(HL)(OAc)(2)](2-) are connected by four M2+ ions (M5). The tetranuclear unit itself can be derived from an ideal C-2 symmetrical [M-4(HL)(2)(mu-eta(2)-OAc)(4)(mu-eta(1),eta(1)-OAc)(2)(eta(1),eta(1)-OAc)](-) structure through deprotonation of the HL- ligand, and is composed of two plane shared M3O4 incomplete cubanes in which the M2 and M3 atoms are involved in the central fused plane and the M1 and M4 atoms are disposed at the apex sites. Mixed-metal icosanuclear complexes [NixM20-xL4(HL)(4)(OAc)(28)] (3, M = Co, x = 9.5) and [Ni12M8L4(HL)(4)(OAc)(28)] (4, M = Cu) were also synthesized by using equimolar amounts of Ni-II and ions, and were shown to have similar structures to 1 and 2. X-ray crystallographic and fluorescent analyses revealed that complex 3 contains nonstoichiometric amounts of Ni2+ and Co2+ ions in the ratio of 9.5:10.5 and that these are disordered at every metal site. In striking contrast, complex 4 has a stoichiometric formula of Ni12Cu8, which was confirmed by the Jahn-Teller elongation of Cu2+ ions, and consequently, the M2 and M5 positions are occupied exclusively by the Cu2+ ions. The temperature-dependent direct current (dc) magnetic susceptibility data showed the presence of ferromagnetic exchange interactions in the Ni homometallic (1) and NiCu bimetallic (4) complexes, while the Co homometallic (2) and NiCo bimetallic (3) complexes exhibited antiferromagnetic interactions due to spin-orbit coupling effects of the octahedral Co-II ions. The present results demonstrate that the unsymmetrical aminoalcohol ligand H2L is quite effective in organizing the homo- and heterometallic icosanuclear wheel-shaped metal arrangements., 2012年11月, INORGANIC CHEMISTRY, 51 (22), 12503 - 12510, doi;web_of_science

    研究論文(学術雑誌)

  • Structural, photophysical, and mesomorphic properties of luminescent platinum(II)-salen Schiff base complexes

    Yuriko Abe; Yuko Takagi; Miyuki Nakamura; Takae Takeuchi; Tomoaki Tanase; Miho Yokokawa; Hidetomo Mukai; Takashi Megumi; Ayaha Hachisuga; Kazuchika Ohta

    A series of square planar platinum(II) salen complexes containing 4-substituted alkoxy chains of aromatic rings, [Pt((4-CnH2n+1O)(2)salen)] (n = 3 (1), 4 (2), 6 (3), 8 (4), 10 (5), 12 (6), 14 (7), 16 (8), and 18 (9)) has been prepared, and photophysical and mesomorphic properties have been investigated. Complexes 1-9 emitted intense phosphorescence from the mixed exited-state between the MLCT (MLCT = metal-to-ligand charge transfer) and LLCT (LLCT = ligand-to-ligand charge transfer) states both in dichloromethane solution and in solid states at room temperature. The red-shifted solid-state emission spectra from monomers in solution are caused by the supramolecular contact with one-dimensional stacking between neighboring chromophores (salen moieties) through the weak C-H center dot center dot center dot O type hydrogen bonding and van der Waals interactions in the solid state revealed by an X-ray crystallographic analysis for 2. Though 1-4 did not exhibit any mesophases (liquid-crystalline phases), 5-9 showed a lamello-columnar (Col(L)) mesophase with the high thermal stability, leading to the different phosphorescence spectra from both in solution and in solid states. This is affiliated with the appearance of the intermolecular d(z2)PtdII - d(z2)Pt(II) orbital interaction in a one-dimensional stacking distance with ca. 3.0 angstrom due to self-assemblies in the liquid crystal which gives rise to the MMLCT (MMLCT = metal-metal-to-ligand charge transfer) transition. This is supported by absorption and emission measurements in the wide range from room temperature in the solid state to the clearing points (around 280 degrees C). The relationship between molecular assemblies and photophysical properties is discussed. (C) 2012 Elsevier B. V. All rights reserved., 2012年09月, INORGANICA CHIMICA ACTA, 392, 254 - 260, doi;web_of_science

    研究論文(学術雑誌)

  • Hydride-Bridged NiRh Complexes with Tunable N3S2 Dithiolato Ligands and Their Utilization as Catalysts for Hydrogenation of Aldehydes and CO2 in Aqueous Media

    Bunsho Kure; Ayami Taniguchi; Takayuki Nakajima; Tomoaki Tanase

    New N3S2 dithiolato ligands, 1,4-bis(2-mercaptoethyl)-7-R-1,4,7-triazacyclononane (RTACN-S2H2; R = Ts, Pr-i) were synthesized and reacted with Ni-II ion to give mononuclear complexes [Ni(RTACN-S-2)] (R = Ts (1a), Pr-i (1b)). Complexes 1a and 1b were further transformed by treatment with Rh-III species into a series of (NiRhIII)-Rh-II heterodimetallic compounds, [Ni(RTACN-S-2)RhCp*X]X' (R = Ts, X = Cl, X' = Cl, OTf ([2a]X'); R = Ts, X = X' = NO3 ([3a]NO3); R = Pr-i, X = Cl, X' = Cl, NO3, PF6 ([2b]X')). Complexes [3a]NO3 and [2b]NO3 were readily reacted with H-2 (0.1 MPa) in water at room temperature to afford hydride-bridged (NiRhIII)-Rh-II dinuclear complexes, [(RTACN-S-2)Ni(mu-H)RhCp*]NO3 (R = Ts ([4a]NO3), Pr-i ([4b]NO3)), which were successfully characterized by X-ray crystallography. Upon the heterolytic activation of H-2, the Ni-Rh interatomic distances were dramatically decreased from 3.2130(6)-3.262(2) angstrom ([2a]OTf, [2b]NO3, [3a]NO3) to 2.6921(6)-2.7228(4) angstrom ([4a]NO3, [4b]NO3), resulting in semibridging Ni(mu-H)Rh cores. In addition, the stability of the hydride of [4a](+) and [4b](+) were interestingly tuned by varying the R group of the TACN ligand through trans influence at the Ni-II center (Ni-NR=2.188(3) angstrom ([4a(+)]), 2.056(2) angstrom ([4b](+)). In fact, [4a](+) was quite stable and capable of reducing benzaldehyde in water, although [4b] quickly decomposed under similar conditions. Catalytic hydrogenation of aldehydes and CO2 in water has been established by using [3a]NO3 and [2a]Cl as precursors of an active species, [4a](+), and found to be interestingly contrasted to the inactive precursor [2b]NO3 with R = Pr-i. These results indicated that the properties and reactivity of the Ni(mu-H)Rh complexes can be controlled by changing the substituents of the N3S2 supporting ligands., 2012年07月, ORGANOMETALLICS, 31 (13), 4791 - 4800, doi;web_of_science

    研究論文(学術雑誌)

  • Cyclic Trinuclear Rh2M Complexes (M = Rh, Pt, Pd, Ni) Supported by meso-1,3-Bis[(diphenylphosphinomethyl)phenylphosphino]propane

    Takayuki Nakajima; Sachi Kurai; Sayo Noda; Maki Zouda; Bunsho Kure; Tomoaki Tanase

    Reaction of [MCl2(cod)] (M = Pd, Pt) with a tetraphosphine, meso-1,3-bis[(diphenylphosphinomethyl)phenylphosphino]propane (dpmppp), afforded the mononuclear complexes [MCl2(dpmppp)] (M = Pd (3a), Pt (3b)), in which the dpmppp ligand coordinated to the M ion by two inner phosphorus atoms to form a six-membered chelate ring with two outer phosphines uncoordinated. The pendant outer phosphines readily reacted with [RhCl(CO)(2)](2) to give the cationic heterotrinuclear complexes [MRh2(mu-Cl)(3)(mu-dpmppp) (CO)(2)]X (X = [RhCl(CO)(2)](2), M = Pd (4a), Pt (4b); X = PF6, M = Pd (5a), Pt (5b)). The nickel analogue [NiRh2(mu-Cl)(3)(mu-dpmppp)(CO)(2)]PF6 (5c) was also prepared. A neutral homotrinuclear Rh-3 complex, [Rh-3(mu-Cl)(3)(mu-dpmppp)(CO)(2)] (6), was synthesized by the reaction of [RhCl(CO)(2)](2) with dpmppp and was further reacted with HgX2 (X = Cl, Br, I) to afford the Rh3Hg tetranuclear complexes [Rh-3(HgX)(mu-Cl)(2)(mu-X)(mu-dpmppp)(CO)(2)]PF6 (X = Cl (7a), Br (7b), I (7c)), where the Rh-3(mu-Cl)(2)(mu-X) cores act as tridentate ligands to form three donor-acceptor Rh -> Hg interactions. The two CO ligands of 7a-c were replaced by XylNC to yield [Rh-3(HgX)(mu-Cl)(2)(mu-X)(mu-dpmppp)(XylNC)(2)]PF6 (X = Cl (8a), Br (8b), I (8c)). The isocyanides had an appreciable influence on the three Rh -> Hg interactions, which was monitored by the (2)J(Hgp) values observed in the P-31{H-1} NMR spectra and discussed on the basis of DFT calculations. Complex 6 also reacted with CuCl and HBF4 to give [Rh-3(CuCl)(mu-Cl)(3)(mu-dpmppp)(CO)(2)] (9) and [Rh-3(mu(3)-H)(mu-Cl)(3)(mu-dpmppp)(CO)(2)]BF4 (10), respectively. These results suggested that the new tetraphosphine dpmppm proved quite useful in constructing fine-tunable heterometallic frameworks., 2012年06月, ORGANOMETALLICS, 31 (11), 4283 - 4294, doi;web_of_science

    研究論文(学術雑誌)

  • Heterotrinuclear Complexes with Palladium, Rhodium, and Iridium Ions Assembled by Conformational Switching of a Tetraphosphine Ligand around a Palladium Center

    Akiko Yoshii; Hiroe Takenaka; Hiroko Nagata; Sayo Noda; Kanako Nakamae; Bunsho Kure; Takayuki Nakajima; Tomoaki Tanase

    Reaction of [PdCl2(cod)] with a tetraphosphine, meso-bis[((diphenylphosphino)methyl)phenylphosphino]methane (dpmppm), afforded the mononuclear Pd-II complexes [PdCl(dpmppm-kappa(3))]X (X = Cl (la), PF6 (1b)); the pincer-type dpmppm ligand coordinates to the Pd atom with two outer and one inner phosphorus atom to form fused six- and four-membered chelate rings. The remaining inner phosphine is uncoordinated and readily reacts with [CP*MCl2](2) to give the heterodimetallic complexes [PdCl-(Cp*MCl2)(mu-dpmppm-kappa(3),kappa(1))]X (X = Cl, M = Rh (21a), Ir (21b); X = PF6, M = Rh (23a), Ir (23b)). Attachment of the second metal fragment to the uncoordinated phosphine caused a crucial conformational change of the six-membered chelate ring from a stable chair conformation to a twist-boat structure, which concomitantly destabilizes the four-membered ring for its opening reactions. Complexes 21 (X = Cl) were converted to [PdCl2(Cp*MCl2)(dpmppm=O)], in which the terminal P atom is dissociated and oxidized as Ph2P(=O)CH2P(Ph)CH2P(Ph)CH2PPh2 (dpmppm=O), and in the presence of another 1 equiv of [Cp*M'Cl-2](2), complexes 21 were readily transformed into the heterotrinuclear complexes [PdCl2(Cp*M'Cl-2)(Cp*MCl2)(mu-dpmppm-kappa(2),kappa(1),kappa(1))] (M = M' = Rh (31a), Ir, (31b); M = Ir, M' = Rh (31c)), where the third metal M' is trapped by the terminal P atom with its four-membered-ring opening. Complexes 23 also reacted with another 1 equiv of [Cp*M'Cl-2](2) to afford the heterotrinuclear complexes [PdCl(mu-Cl)(Cp*M'Cl)(Cp*MCl2)(mu-dpmppm-kappa(2),kappa(1),kappa(1))]PF6 (M = M' = Rh (32a), Ir, (32b); M = Ir, M' = Rh (32c), M = Rh, M' = Ir (32d)); the additional metal M' is ligated by the terminal phosphine and is further connected to the Pd atom via a chloride bridge, resulting in a rather electron-deficient M' center on the basis of cyclic voltammetry. These results exhibited that the addition of a bulky metal fragment to the uncoordinated phosphine of 1 brings about a conformational switch around the Pd center to promote the ring-opening reaction of the four-membered chelate ring, which leads to an incorporation of the third metal fragment to construct heterotrinuclear structures., 2012年01月, ORGANOMETALLICS, 31 (1), 133 - 143, doi;web_of_science

    研究論文(学術雑誌)

  • Heterotrinuclear Complexes with Pd, Rh, and Ir Ions Assembled by Conformational Switch of a Tetraphosphine Ligand around Pd Center

    A. Yoshii; H. Takenaka; H. Nagata; S. Noda; K. Nakamae; B. Kure; T. Nakajima; T. Tanase

    2012年, Organometallics, 31, 133-143

  • Octanuclear Iron(III) Complexes Supported by Kemp’s Tricarboxylate Ligands

    Yukie Takemura; Yayoi Okui; Bunsho Kure; Takayuki Nakajima; Tomoaki Tanase; Masahiro Mikuriya; Masashi Takahashi

    Reactions of FeCl2 center dot 4H(2)O and diimino ligand (L) with H(3)kta (cis,cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid) in the presence of [(Bu4N)-Bu-n][OH] afforded a series of octanuclear iron(III) complexes formulated as [Fe8O5(kta)(2)(Hkta)(4)(L)(2)] (L = bpy (1), 5,5'-Me(2)bpy (2), 4,4'-Me(2)bpy (3), phen (4), 4-Mephen (5), 4,7-Me(2)phen (6), and 3,4,7,8-Me(4)phen (7)). The structure of 4 was determined by X-ray crystallography to consist of a planar {Fe-8(mu(4)-O)(mu(3)-O)(4)}(14+) core supported by two kta(3) tricarboxylates, where the inner four Fe-III ions form a {Fe4O5} square plane, of which apex mu-oxo atoms are further connected to the outer four Fe-III ions. The peripheral part of the Fe-8 core is bridged by four Hkta(2) ligands and chelated by two phen ligands. Fe-57 Mossbauer spectra of 2 at 290 K and 77 K indicated the presence of high-spin octahedral Fe(III) ions, and the temperature dependent dc magnetic susceptibility data for 1, 2, and 4 showed strong antiferromagnetic exchange in the {Fe8O5} moiety. (C) 2011 Elsevier B.V. All rights reserved., 2011年12月, INORGANICA CHIMICA ACTA, 379 (1), 100 - 108, doi;web_of_science

    研究論文(学術雑誌)

  • Intramolecular Metal-Metal Bond Rearrangement in a Pt2PdHg Heterometallic Cluster Forming a Hg-I-Pd-I Covalent Bond

    Aya Hosokawa; Bunsho Kure; Takayuki Nakajima; Kanako Nakamae; Tomoaki Tanase

    Reaction of the linear trinuclear complex [Pt2M(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (M = Pd (1b)) with HgX2 afforded the Pt2PdHg mixed-metal complexes [Pt2PdHgX2(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (X = Cl (2), Br (3), I (4)), which included an unprecedented Hg-I-Pd-I covalent bond formed via intramolecular metal-metal bond rearrangement. In contrast, reaction of 1a (M = Pt) with HgCl2 afforded the novel pentagonal-shaped Pt3Hg3 planar cluster [Pt3Hg3Cl4(mu-dpmp)(2)(XylNC)(2)]Cl-2(PF6)(2) (5)., 2011年11月, ORGANOMETALLICS, 30 (22), 6063 - 6066, doi;web_of_science

    研究論文(学術雑誌)

  • Tetrapalladium Complex with Bridging Germylene Ligands. Structural Change of the Planar Pd4Ge3 Core

    Tanabe, Makoto; Ishikawa, Naoko; Chiba, Mai; Ide, Tomohito; Osakada, Kohtaro; Tanase, Tomoaki

    A complex with a planar hexagonal Pd4Ge3 core, [Pd{Pd(dmpe)}(3)(mu(3)-GePh2)(3)], was synthesized and characterized by X-ray and NMR measurements as well as by DFT calculations. 4-tert-Butylbenzenethiol converted the Pd-4 complex into a hexapalladium complex, [{Pd-3(mu-GePh2)(2)-(mu-H)(mu(3)-GePh2((SC6H4Bu)-Bu-t-4))}(2)(mu-dmpe)], composed of two Pd3Ge3 units bridged by a dmpe ligand. The addition of CuI or AgI to the Pd-4 complex yielded [Pd(mu-MI){Pd-(dmpe)}(3)(mu(3)-GePh2)(3)] (M = Cu, Ag), in which Cu or Ag bridges a Pd-Pd bond of the Pd4Ge3 core. The CuI adducts in solution undergo a pivot motion of the CuI on the surface of the Pd4Ge3 plane on the NMR time scale, 2011年11月, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133 (46), 18598 - 18601, doi;web_of_science

    研究論文(学術雑誌)

  • Systematic Expansion of Supercubane Cores in Manganese Oxo Clusters with Tricarboxylate Ligands

    Yayoi Okui; Florina Aurelia Catusanu; Ryoko Kubota; Bunsho Kure; Takayuki Nakajima; Tomoaki Tanase; Takashi Kajiwara; Masahiro Mikuriya; Hitoshi Miyasaka; Masahiro Yamashita

    A novel class of high-nuclearity Mn-17 and Mn-19 mixed-valent complexes, [Mn-17(mu-O)(12)(mu-OMe)(2)(mu-kta)(6)(MeOH)(4)] (1), [Mn-17(mu-O)(14)(mu-kta)(6)L-4] [L = bpy (2a), phen (2b), 4,7-Ph(2)phen (2c), dmf (3)], and [Mn-19(mu-O)(14)(mu-kta)(6)(bpy)(6)]X-3 [X = PF6 (4a), BF4 (4b)], were synthesized by utilizing Kemp's tricarboxylate ligands (H(3)kta = cis,cis-1,3,5-trimethylcyclohexane-1,3,5- tricarboxylic acid). The complexes were characterized by X-ray crystallography and reveal mineralomimetic Mn-13 supercubane units, [Mn-13(mu-O)(14)], in which their oxidation states systematically altered, depending on their vertex face-capping ligands and Mn-II satellite fragments. Complex 2a was converted by treatment with benzoic acid and [Mn2O2(bpy)(4)](BF4)(3) to a cage-type Mn-14 complex, [Mn-14(mu-O)(12)(mu-OH)(6)(mu-Hkta)(6)(bpy)(6)](BF4)(4) (5), which show ferro- and antiferromagnetic interactions and slow magnetic relaxation at low temperature., 2011年10月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (28), 4325 - 4330, doi;web_of_science

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  • Stepwise Construction of Au4Ag2Cu2 Coinage Rings Supported by Linear Tetraphosphine Ligands

    Yukie Takemura; Tomoko Nishida; Bunsho Kure; Takayuki Nakajima; Masayasu Iida; Tomoaki Tanase

    2011年09月, CHEMISTRY-A EUROPEAN JOURNAL, 17 (38), 10528 - 10532, doi;web_of_science

    研究論文(学術雑誌)

  • Development of Molecular Metal Chains Supported by Multidentate Phosphines

    T. Tanase

    2010年, Bull. Jpn. Soc. Coord. Chem. (Account), 55, 52-70

  • Chemically Modified Electrode with a Film of Nano Ruthenium Oxides Stabilizing High Valent RuO4- Species and Its Redox-Selective Sequential Transformation to Polynuclear Ruthenium Oxide-Metallocyanates

    Annamalai Senthil Kumar; Tomoaki Tanase; Jyh-Myng Zen

    High-valent (RuO4-)-O-VII (perruthenate) is a short-lived species in aqueous solutions (pH 1-14) and has scarcely been studied through electrochemistry. By a potential-controlled oxidative deposition method at I V vs Ag/AgCl using RuCl3 in a pH 2 KCl-HCl buffer solution, chemically modified glassy carbon (GCE) and indium tin oxide (ITO) electrodes were successfully prepared with a Film of hydrous nano ruthenium oxides RuO2 and RuO3, stabilizing the high-valent perruthenate anion (Ru(VII)-RuOx-CME, x = 2 and 3, CME = chemically modified electrode). The electrodes showed three distinct redox peaks corresponding to Ru2O3/RuO2, RuO2/RuO3, and RuO42-/RuO4- redox processes at pH 2, like the classical RuO2 electrodes in alkaline conditions. Solid state UV-visible spectra of the ITO/Ru(VII)-RuOx-CME showed characteristic absorption very close to chemically generated authentic RuO4 species in alkaline solution. Further, redox-controlled sequential procedures yielded polynuclear ruthenium oxide-hexacyanometallate films (RuOMCN-CME, M = Fe and Ru), in which Ru(VII)-RuOx-CME acted as a specific template. A controlled-potential activation (> 1 V) of Ru(VII)-RuOx-CME, stabilizing the key RuO4- species, in a solution of [Fe(CN)(6)](3-) or [Ru(CN)(6)](4-), should be a critical step for the formation of polynuclear RuO-MCN matrix., 2009年12月, LANGMUIR, 25 (23), 13633 - 13640, doi;web_of_science

    研究論文(学術雑誌)

  • Synthesis and Characterization of Linear Tetranuclear Silver(I) Complexes Bridged by Tetraphosphane Ligands

    Yukie Takemura; Takayuki Nakajima; Tomoaki Tanase

    Reactions of AgOTf with meso-bis[(diphenylphosphanylmethyl)phenylphosphanyl]methane (dpmppm) afforded [Ag(4)(OTf)(2)(m-OTf)(m-dpmppm)(2){(CH(3))(2)CO}](OTf) (1) and [Ag(4)(OTf)(2)(m-OTf)(m-dpmppm)(2)(RNC)(2)](OTf) [R = Xyl (2a), Mes (2b), tBu (2c)}. When AgOTf was treated with dpmppm in air in the presence of tBuNC, cleavage of the C-Cl and P-C bonds occurred to give [Ag(4)(m-Cl)(m-dpmppm)(2)(tBu-NC)(4)](OTf)(3) (3) and [Ag(4)(m-Ph(2)PO(2))(m-dpmppm)(2)(tBuNC)3]-(OTf)(3) (4). Reaction of AgOCOCF(3) with dpmppm resulted in [Ag(4)(OCOCF(3))(2)(m-OCOCF(3))(m-dpmppm)(2)](CF(3)COO) (5). By treatment of AgPF(6) with dpmppm, [Ag(4)(m-dpmppm)(2)-(tBuNC)(4)](PF(6))(4) (6) and [Ag(4)(PO(2)F(2))(2)(m-dpmppm)(2)(tBuNC)(2)] (PF(6))(2) (7) were obtained. Wheareas complexes 1-3 possess a [Ag(4)(m-dpmppm)(2)](4+) core in which the Ag(4) strings are rather bent with two dpmppm ligands arranged in a syn fashion, complexes 4-7 have linear Ag(4) strings supported by two dpmppm ligands arranged in an anti fashion. These results suggest that the dpmppm -supported tetrasilver(I) strings are quite flexible and labile and thus are potentially important in promoting organic reactions as a result of the multimetallic centers. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009), 2009年11月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (32), 4820 - 4829, doi;web_of_science

    研究論文(学術雑誌)

  • Planar Tetranuclear and Dumbbell-Shaped Octanuclear Palladium Complexes with Bridging Silylene Ligands

    Yamada, Tetsuyuki; Mawatari, Akane; Tanabe, Makoto; Osakada, Kohtaro; Tanase, Tomi

    2009年, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48 (3), 568 - 571, doi;web_of_science

    研究論文(学術雑誌)

  • Dynamic structural changes of pentacopper(II) chains supported by N-6-donor ligands

    Yukie Takemura; Takayuki Nakajima; Tomoaki Tanase; Miho Usuki; Hiroe Takenaka; Eri Goto; Masahiro Mikuriya

    Elastic pentacopper molecular chains, [Cu-5(panapy)(4)X-2] (X = Cl (1), Br (2)) and [Cu-5(panapy)(4)]X'(2) (X' = BF4 (3), PF6 (4)), were prepared using a naphthyridine-modulated N-6-donor ligand, panapy(2-), and showed magnetically coupled, dynamic rearrangement of five Cu(II) ions switched by the presence/absence of halide termination., 2009年, CHEMICAL COMMUNICATIONS, (13), 1664 - 1666, doi;web_of_science

    研究論文(学術雑誌)

  • Hexa- and Octagold Chains from Flexible Tetragold Molecular Units Supported by Linear Tetraphosphine Ligands

    Yukie Takemura; Hiroe Takenaka; Takayuki Nakajima; Tomoaki Tanase

    2009年, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48 (12), 2157 - 2161, doi;web_of_science

    研究論文(学術雑誌)

  • Interconversion between ladder-type octanuclear and linear tetranuclear copper(I) complexes supported by tetraphosphine ligands

    Yukie Takemura; Takayuki Nakajima; Tomoaki Tanase

    Linearly ordered tetraphosphine, meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane(dpmppm), readily reacted with 4 equiv. of CuX in dichloromethane to afford octanuclear copper(I) complexes, [Cu(8)(mu-X)(8)(mu-dpmppm)(2)] (X = Cl (1a), Br (1b), I (1c)), which involve a ladder-type {Cu(8)(mu-X)(2)(mu 3-X)(6)} core supported by two dpmppm ligands in anti arrangement. Complex 1a was further transformed by treatment with Cu(OTf)(2) into [Cu(8)(mu-X)(6)(OTf)(2)(mu-dpmppm)(2)] (2) in which two TfO anions attached to both end of the Cu(8) ladder. When complexes 1 were dissolved in dimethyl sulfoxide (dmso) in the presence of 2 equiv. of dpmppm, the octacopper(I) ladder was unzipped to result in the linear tetranuclear copper(I) complex, [Cu(4)X(mu-X)(3)(mu-dpmppm)(2)(dmso)] (X = Cl (3a), Br (3b), I (3c)). Similar treatment of dpmppm with 2 equiv. of CuX in the presence of coordinative solvents, N,N'-dimethylformamide (dmf) and pyridine (py), yielded the symmetrical tetracopper(I) complexes, [Cu(4)(mu-Cl)(3)(mu-dpmppm)(2)(dmf)(2)][CuCl(2)] (4) and [Cu(4)(mu-I)(3)(mu-dpmppm)(2)(py)(2)]I (5). A series of tetracopper(I) complexes with terminal isocyanide ligands, [Cu(4)(mu-X)(3)(mu-dpmppm)(2)(RNC)(2)]PF(6) (X = Cl, R = Xyl (6a); X = Br, R = Mes (7b); X = I, R = Xyl (8a), Mes (8b), (t)Bu (8c)), were obtained from reactions of dpmppm with 2 equiv. of CuX in dmf or acetonitrile followed by addition of an excess of RNC and NH(4)PF(6). Complexes 3-8 possess a bending Cu(4)(mu-X)(3) chain supported by two dpmppm ligands in syn arrangement, where the terminal sites are reactive and accommodate a variety of terminal ligands. When complex 8c was treated with AgPF(6) in a CH(3)CN-CH(2)Cl(2) mixed solvent, the soft Lewis acidic Ag(I) ions took the copper(I)-binding dpmppm off and the resultant two {Cu(4)(mu-I)(3)(mu-dpmppm)((t)BuNC)(2)}(+) fragments were zipped up to form the ladder-type octacopper(I) complex, [Cu(8)(mu-I)(6)(mu-dpmppm)(2)((t)BuNC)(2)](PF(6))(2) (9). The apparent interconversion between the Cu(8) ladder and the Cu(4) chain might proceed through a labile intermediate with a {Cu(4)(mu-X)(3)(mu-dpmppm)}(+) unit, which could be useful synthon of further extended copper(I) halide clusters., 2009年, DALTON TRANSACTIONS, (46), 10231 - 10243, doi;web_of_science

  • N-Glycoside Complexes of Nickel(II); Probing Carbohydrate-Transition Metal Interactions

    Dale Jones; Marcelis van Holst; Shigenobu Yano; Tomoaki Tanase; Janice Aldrich-Wright

    Nickel(II) complexes prepared from D- and L-arabinose (D-ara and L-ara) and 1,2-diaminoethane (en), [Ni(en-D-ara)(2)](ClO4)(2)center dot 2H(2)O 1 and [Ni(en-L-ara)(2)](ClO4)(2)center dot 2H(2)O(2) (where en-D-ara is 1-((2-aminoethyl)amino)-1-deoxy-D-arabinose) were synthesized and characterized by absorption spectroscopy, circular dichroism (CD), and X-ray crystallography. The CD spectra of 1 and 2 in the d-d transition region indicate a C-2 chiral configuration around the metal centre. X-ray crystallography of 1 revealed that two 1-((2-aminoethyl)amino)-1-deoxy-D-arabinose ligands coordinate to the nickel atom in nearly C-2 symmetry, through the C(2) hydroxy group of the arabinose moiety and two nitrogen atoms of the diamine in a meridional mode. This results in a Lambda-C-2-helical configuration around the metal centre. The arabinose ring adopts the rare alpha-C-1(4) chair conformation and the carbohydrate-chelate ring conformation is delta., 2009年, AUSTRALIAN JOURNAL OF CHEMISTRY, 62 (3), 265 - 268, doi;web_of_science

    研究論文(学術雑誌)

  • Synthesis, structures and ion-association properties of a series of Schiff base Oxidovanadium(V) complexes with 4-substituted long alkoxy chains

    Yuriko Abe; Ayako Iyoda; Kanako Seto; Ayano Moriguchi; Tomoaki Tanase; Haruhiko Yokoyama

    Schiff base VO(2)(V) and VO(V) complexes with long 4-substituted alkoxy chains have been synthesised from the corresponding VO(IV) complexes, [VO{(4-C(n)H(2n+1))(x)salen}] [x = 1, 2, n = 3-16 and salen = N,N'-ethylenebis(salicylideneiminato)], in solutions in the absence or presence of HClO(4) under aerobic conditions. The green single-crystals of the VO(IV) complexes (x = 2, n = 3, 4, 6) coexisting with solutions without HClO(4) turned slowly to the yellow single-crystals of the species with n = 3 (1) and 4 (2), a process which took several months. An X-ray crystallographic analysis revealed that the VO(IV) complexes are transformed into the dimeric VO(2)(V) complexes with the tridentate sal-en (sal-en = N-salicylidene-ethylenediamine) ligand from the tetradentate salen moieties. However, the single crystals of the VO(IV) complexes with longer alkoxy chains of n 8 did not yield the corresponding yellow crystals of the VO(2)(V) complexes. This crystal-to-crystal transformation is discussed in relation to the crystal packing structures of the VO(IV) complexes. In contrast, addition of HClO(4) solution to two series with one and two alkoxy chains in the 4-positions immediately afforded the corresponding blue VO(V) perchlorate complexes, [VO{(4-C(n)H(2n+1)O)(x)salen}]-ClO(4) (X = 1, 2) without transformation of the salen moieties. The structure of 8 center dot MeOH center dot 0.5H(2)O determined from an X-ray crystallographic analysis was a unique dimeric structure supported by electrostatic stacking and CH-pi interactions in an octahedral environment. The DFT calculations were studied to obtain the stabilisation energy for the dimerisation. Furthermore, in methanol solution, the effects of the alkoxy chain lengths on the ion association were investigated by conductivity measurements. The ion-association state in methanol solution is discussed with the solid-state structure. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)., 2008年05月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (13), 2148 - 2157, doi;web_of_science

    研究論文(学術雑誌)

  • Dinuclear Rh(I) complex with 2,7-bis(diphenylphospl-lino)1,8-naphthyridine: Synthesis, structure, and dynamic property

    Tomoaki Tanase; Hiroe Takenaka; Eri Goto

    Reaction of [RhCl(cod)](2) with 2,7-bis(diphenylphosphino)-1,8-naphthyridine (dpnapy) and 2,6-xylyl isocyanide (XylNC) in the presence of NH4PF6 afforded the dirhodium(I) complex, [Rh-2(mu-dpnapy)(2)(XylNC)(4)](PF6)(2) (5), and similar procedures using [MCl2(cod)] (M = Pt, Pd) resulted in the formation Of [Pt-2(mu-dpnapy)(2)(XylNC)(4)](PF6)(4) (6) and [Pd2Cl2(mu-dpnapy)(2)(XylNC)(2)](PF6)(2) (7). Complexes 5-7 were characterized by elemental analysis, IR, UV-Vis, H-1 and P-31{H-1} NMR, and ESI mass spectroscopic techniques, to involve a small and rigid d(8) {M-2(mu-dpnapy)(2)} metallomacrocycle. Complex 5 readily incorporated a silver(I) ion into the macrocycle to afford [Rh2Ag(mu-dpnapy)(2)(XylNC)(4)](PF6)(3) (8) which was characterized by X-ray crystallography. The Ag(I) ion is trapped by two trans N atoms of dpnapy ligands, resulting in an asymmetric Rh-Ag center dot center dot center dot Rh structure, determined as a disordered model in the crystal structure, and however, in a CH2Cl2 solution, a dynamic interconversion of the two Ag-trapped sites was observed with low-temperature NMR studies, which was further supported by DFT molecular orbital calculations. When an acetonitrile solution of complex 5 was treated over a droplet of mercury(0), the polymeric compound formulated as {[Rh(mu-dpnapy)(XylNC)(2)](PF6)}(n) (9) was isolated as yellow single crystals, which were revealed by X-ray crystallography to consist of C-6 helical rods along c axis with a pitch of 33.5 angstrom (rise of unit = 5.6 angstrom) and a diameter of 20.64 angstrom. (c) 2006 Elsevier B.V. All rights reserved., 2007年01月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 692 (1-3), 175 - 183, doi;web_of_science

    研究論文(学術雑誌)

  • In situ nanostructure formation of (mu-hydroxo)bis(mu-carboxylato) diruthenium units in nafion membrane and its utilization for selective reduction of nitrosonium ion in aqueous medium

    Annamalai Senthil Kumar; Tomoaki Tanase; Masayasu Iida

    Nanostructured molecular film containing the (mu-hydroxo)bis(mu-carboxylato) diruthenium(III) units, [Ru-2(III)(mu-OH)(mu-CH3COO)(2)(HBpz(3))(2)](+) ({Ru-2(III)(mu-OH)}), was prepared by an in situ conversion of its mu-oxo precursor, [Ru-2(III)(mu-O)(mu-CH3COO)(2)(HBpz(3))(2)] ({Ru-2(III)(mu-O)}), in a Nafion membrane matrix, where HBpz(3) is hydrotris(1-pyrazolyl)borate. The conversion procedure results in fine nanoparticle aggregates of the {Ru-2(III)(mu-OH)} units in the Nafion membrane (Nf-{Ru-2(III)(mu-OH)}), where an average particle size (4.1 +/- 2.3 nm) is close to the Nafion's cluster dimension of similar to 4 nm. Chemically modified electrodes by using the Nafion molecular membrane films (Nf-{Ru-2(III)(mu-OH)}-MMFEs) were further developed on ITO/glass and glassy carbon electrode (GCE) surfaces, and a selective reduction of nitrosonium ion (NO+), presumably through reaction of a {(RuRuIII)-Ru-II(mu-OH)} mixed-valence state with HNO2, was demonstrated without interference by molecular oxygen in an acidic aqueous solution. The Nf-{Ru-2(III)(mu-OH)}-MMFEs are stable even in a physiological condition (pH 7), where the naked {Ru-2(III)(mu-OH)} complex is readily transformed into its deprotonated {Ru-2(III)(mu-O)} form, demonstrating an unusual stabilizing effects for the {Ru-2(III)(mu-OH)} unit by the Nafion cluster environment., 2007年01月, LANGMUIR, 23 (2), 391 - 394, doi;web_of_science

    研究論文(学術雑誌)

  • Syntheses, structures, and mesomorphism of a series of Cu(II) salen complexes with 4-substituted long alkoxy chains

    Y. Abe; N. Nakazima; T. Tanase; S. Katano; H. Mukai; K. Ohta

    A series of copper(II) salen complexes containing 4-substituted alkoxy chains of aromatic rings [Cu((4-CnH2n+1O)(2)salen)] (n = 3 (1), 4 (2), 6 (3), 8 (4), 10 (5), 12 (6), 14 (7), 16 (8), 18 (9), and 20 (10) and salen (N, N'-ethylenebis(salicylideneiminato)) has been prepared, and single-crystal structures of 2 center dot H2O, 4, and 6 by an X-ray crystallographic analysis have been revealed. Complexes 4 and 6 form tetrahedrally distorted square planer structure with one-dimensional polymeric stacking by van der Waals interaction between the dramatically distorted salen moieties. Complexes 1-3 did not exhibit any mesophases, but complexes 4-10 with longer alkoxy chains of n = 8-20 showed the metallomesogen of a lamello-columnar (ColL) mesophase in the smectic layers with the nearly constant stacking distances, irrespective of the variation of the alkoxy chain lengths by the X-ray diffraction measurements, which show similar behaviors to the corresponding Ni(II) complexes of n = 14-20. The molecular assemblies and mesomorphic properties in relation to the single-crystal structures of 4 and 6 with the liquid crystals at higher temperature are discussed., 2007年, MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 466, 129 - 147, doi;web_of_science

    研究論文(学術雑誌)

  • Syntheses, structures, and mesomorphic properties of two series of oxovanadium(IV) salen and salpn complexes with 4-substituted long alkoxy chains

    Yuriko Abe; Kyoko Nakabayashi; Nahoko Matsukawa; Hiroshi Takashima; Masayasu Iida; Tomoaki Tanase; Makiko Sugibayashi; Hidetomo Mukai; Kazuchika Ohta

    Two series of oxovanadium(IV) salen and salpn complexes containing 4-substituted alkoxy chains of aromatic rings, [VO((4-CnH2n+1O)(2)salen)] (n = 3 (1), 4 (2), 6 (3), 8 (4), 10 (5), 12 (6), 14 (7), 16 (8), 18 (9), and 20 (10) and salen = N,N'-ethylenebis(salicylideneiminato)), and [VO((4-CnH2n+1O)(2)salpn)] (n = 8 (11), 10 (12), 12 (13), 14 (14), 16 (15), and 18 (16) and salpn = N,N'-propylenebis(salicylideneiminato)), have been prepared and their mesomorphic properties have been investigated. The crystal structures of 1-9 except for 7 by an X-ray crystallographic analysis have been revealed. Complexes 4-9 in the solid state have been confirmed as novel bilayer crystal structures composed of only the VO(IV) complex without linear chains via the V=O units. The VO(IV) complexes with longer alkoxy chains of 8-10 transferred from the bilayer crystal to the bilayer metallomesogens (liquid crystals). Based on the X-ray analyses and the precise extinction rules for 8-10 with the bilayer metallomesogens, complexes 8-10 were identified as the liquid crystalline (M(Pa2(1))) phase derived from 80 layer groups, On the other hand, the 4-alkoxysalpn complexes of 14-16 showed the unusual rectangular columnar mesophase (Col(Gamma)) with the linear chain via the V=O units supported by the existence of the V=O stretching band characteristic of weak linear chain formation via the V=O units in the liquid crystal. (c) 2006 Elsevier B.V. All rights reserved., 2006年09月, INORGANICA CHIMICA ACTA, 359 (12), 3934 - 3946, doi;web_of_science

    研究論文(学術雑誌)

  • Tetranuclear copper(II) complexes bridged by alpha-D-glucose-1-phosphate and incorporation of sugar acids through the Cu-4 core structural changes

    Merii Kato; Ajay Kumar Sah; Tomoaki Tanase; Masahiro Mikuriya

    Tetranuclear copper(II) complexes containing alpha-(D)-glucose-1-phosphate (alpha-(D)-Glc-1P), [Cu-4(mu-OH){mu-(alpha-(D)-Glc-1P)}(2)-(bpy)(4)(H2O)(2)]X-3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu-4(mu-OH) {mu-(alpha-(D)-Glc-1P)}(2)(phen)(4)(H2O)(2)](NO3)(3) (2) were prepared by reacting the copper(II) salt with Na-2[alpha-(D)-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}(2+) fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu(4)-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C-2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-(D)-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-CA)(2)(bpy)(4)](NO3)(2) [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)(2)] also gave the discrete tetracopper(II) cationic complex [Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-m-C6H4(CH2COO)(CH2COOH))(2)- (bpy)(4)](NO3)(2) (5a) as well as the cluster polymer formulated as {[Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-m-C6H4(CH2COO)(2))-(bpy)(4)](NO3)(2)}(n) (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu-II ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta-(D)-gluconolactone, (D)-glucuronic acid, or (D)-glucaric acid in dimethylformamide resulted in the formation of discrete tetracopper complexes with sugar acids, [Cu-4 {mu-(alpha-(D)-Glc-1P)}(2)(mu-SA)(2)(bpy)(4)](NO3)(2)[SA = (D)-gluconate (6), (D)-glucuronate (7), (D)-glucarateH (8a)]. The structures of 6 and 7 were determined by X-ray crystallography to be almost identical with that of 3 with additional chelating coordination of the C-2 hydroxyl group of (D)-gluconate moieties (6) or the C-5 cyclic O atom of (D)-glucuronate units (7). Those with (D)-glucaric acid and (D)-lactobionic acid afforded chiral one-dimensional polymers, {[Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu(D)-glucarate)(bpy)(4)](NO3)(2)}(n) (8b) and {[Cu-4{mu-(alpha-(D)-Glc-1P)}(2)(mu-(D)-lactobionate)(bpy)(4)(H2O)(2)](NO3)(3)}(n) (9), respectively, in which the (D)-Glc-1P-bridged tetracopper(II) units are connected by sugar acid moieties through the C-1 and C-6 carboxylate O atoms in 8b and the C-1 carboxylate and C-6 alkoxy O atoms of the gluconate chain in 9. When complex 7 containing (D)-glucuronate moieties was heated in water, the mononuclear copper(II) complex with 2-dihydroxy malonate, [Cu(mu-O2CC(OH)(2)CO2)(bpy)] (10), and the dicopper(II) complex with oxalate, [Cu-2(mu-C2O4)-(bpy)(2)(H2O)(2)](NO3)(2) (11), were obtained as a result of oxidative degradation of the carbohydrates through C-C bond cleavage reactions., 2006年08月, INORGANIC CHEMISTRY, 45 (17), 6646 - 6660, doi;web_of_science

  • Syntheses, structures, and mesomorphism of a series of Ni(II) salen complexes with 4-substituted long alkoxy chains

    Yuriko Abe; Hiroko Akao; Yukiko Yoshida; Hiroshi Takashima; Tomoaki Tanase; Hidetomo Mukai; Kazuchika Ohta

    A series of nickel(II) salen complexes containing 4-substituted alkoxy chains of aromatic rings, [Ni((4-CnH2n+1O)(2)salen)] (n = 3 (1), 4 (2), 6 (3), 8 (4), 10 (5), 12 (6), 14 (7), 16 (8), 18 (9), and 20 (10)), and their parent complex, [Ni((4-HO)(2)salen)] (11) (salen = N,N'-ethylenebis(salicylideneiminato)), have been prepared and mesomorphic properties have been investigated. An X-ray crystallographic analysis revealed that complex 11 (.) 2DMF has one-dimensional stacking structure supported by the pi-pi interaction between the six-membered chelate and aromatic rings with the Ni-Ni distances of alternatively 3.3957 and 3.7224 angstrom and that complex 3 is formed by one-dimensional stacking by weak C-H center dot center dot center dot 0 type hydrogen bonded interaction between the five-membered chelate ring and phenoxo atoms of the dramatically distorted salen moieties with the Ni-Ni distance of 5.994 angstrom. Complexes 1-6 did not exhibit any mesophases. On the other hand, complexes 7-10 with longer alkoxy chains of n = 14-20 showed an unusual metallomesogen of a lamello-columnar mesophase within the smectic layers with an interlamellar distance of 31.1 angstrom (7), 33.6 angstrom (8), 37.1 angstrom (9), and 39.5 angstrom (10) and nearly constant stacking distance of 6.19-6.24 angstrom between the inter-dimers, irrespective of the variation of the alkoxy chain lengths by the X-ray diffraction measurements of the liquid crystal. The relationship between molecular assemblies and mesomorphic properties is discussed. (c) 2006 Elsevier B.V. All rights reserved., 2006年07月, INORGANICA CHIMICA ACTA, 359 (10), 3147 - 3155, doi;web_of_science

    研究論文(学術雑誌)

  • Transformation of a tetranuclear copper(II) complex bridged by sugar phosphates into nucleotide-containing Cu-4 aggregations

    Merii Kato; Ajay Kumar Sah; Tomoaki Tanase; Masahiro Mikuriya

    Reaction of [Cu-4(mu-OH){mu-(alpha-D-Glc-1P)}(2)(L)(4)(H2O)(2)]X-3 (1a: L = bpy, X = NO3, alpha-D-Glc-1P U-D-glucopyranose-1-phosphate) with Na-2[H(2)ATP] (ATP adenosine 5'-triphosphate) readily afforded the ATP-bridged tetranuclear copper(II) complex [Cu-4(mu-ATP)(2)(bpy)(4)] (3), which was characterized by X-ray crystallographic analysis to consist of four linearly dispersed (Cu-II(bpy)}(2+) fragments bridged by two triphosphate groups of the ATP tetravalent anions. The sugar and adenine base parts of the ATP moieties are away from the copper(II) centers, but the structure was stabilized by weak intramolecular pi-pi stacking between the ATP purine ring and two bpy ligands and intermolecular hydrogen bonding between the adenine base pairs. The variable-temperature magnetic susceptibility of complex 3 exhibited only weak antiferro-magnetic couplings between the four linearly dispersed Cu-II ions. A similar reaction of 1a or 2 (L = phen, X = NO3) with Na-2[IMP] (IMP = mosine 5'-monophosphate) yielded a different type of tetracopper(II) complex formulated as [Cu-4{mu-(IMP-H)}(2)(L)(4)(H2O)(4)](NO3)(2) [L = bpy (5), phen (6)], in which the IMP moieties are deprotonated at the N-1 position of the nucleobase, forming IMP-H trianions, and four (Cu(bpy)(H2O)}(2+) fragments are connected through the N-1, N-7, and O-6 atoms of the nucleobase and the monodentate 5'-phosphate group. Reaction of 1b (L = bpy, X = Cl) with Na-2[UMP] (UMP = uridine 5'-monophosphate) resulted in a polymeric compound formulated as {[Cu{mu-(UMP-H)}(bpy)(H2O)](2)-[Cu-4(mu-OH){mu-(alpha-D-Glc-1P)}(2)(bpy)(4)(H2O)(2)]Cl}(n) (7). The N-3 deprotonated [UMP-H](3-) anions connect (Cu(bpy)(H2O)}(2+) fragments through the N-3 nitrogen atom and the phosphate oxygen atoms to afford C-2-helical coordination polymers and the tetracopper(ii) complex cations, [Cu-4(mu-OH)(mu-(alpha-D-Glc-1P)}(2)(bpy)(4)(H2O)(2)](3+), are incorporated between the polymer chains with a C-2-chiral arrangement of the {Cu-4(mu-OH)(mu-PO4)(2)(bpy)(4)(H2O)(2)} framework constrained to the A-form through inter- and intramolecular stacking interactions between the bpy ligands., 2006年06月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (12), 2504 - 2513, doi;web_of_science

    研究論文(学術雑誌)

  • Dinuclear copper(II) complexes with {Cu-2(mu-hydroxo)bis(mu-carboxylato)}(+) cores and their reactions with sugar phosphate esters: A substrate binding model of fructose-1,6-bisphosphatase

    M Kato; T Tanase; M Mikuriya

    2006年04月, INORGANIC CHEMISTRY, 45 (7), 2925 - 2941, doi;web_of_science

    研究論文(学術雑誌)

  • Tri- and tetranuclear copper(II) complexes consisting of mononuclear Cu(II) chiral building blocks with a sugar-derived Schiff's base ligand

    AK Sah; T Tanase; M Mikuriya

    A new sugar-derived Schiff's base ligand N-(3-tert-butyl-2-hydroxybenzylidene)-4,6-O-ethylidene-beta-D-glucopyranosylamine (H3L1) has been developed which afforded the coordinatively labile, alcoholophilic trinuclear Cu(II) complex [Cu-3(L-1)(2)(CH3OH)(H2O)] (1). Complex 1 has been further used in the synthesis of a series of alcohol-bound complexes with a common formula of [Cu-3(L-1)(2)(ROH)(2)] (R = Me (2), Et (3), Pr-n (4), Bu-n (5), (n)Oct (6)). X-ray structural analyses of complexes 2-6 revealed the collinearity of trinuclear copper(II) centers with Cu-Cu-Cu angles in the range of 166-172 degrees. The terminal and central coppers are bound with NO3 and O-4 atoms, respectively, and exhibit square-planar geometry. The trinuclear structures of 2-6 can be viewed as the two {Cu(L-1)}(-) fragments capture a copper(II) ion in the central position, which is further stabilized by a hydrogen-bonding interaction between the alcohol ligands and the sugar C-3 alkoxo group. Complex 2 exhibits a strong antiferromagnetic interaction between the Cu(II) ions (J = -238 cm(-1)). Diffusion of methanol into a solution of complex 1 in a chloroform/THF mixed solvent afforded the linear trinuclear complex [Cu-3(L-1)(2)(CH3OH)(2)(THF)(2)] (7). The basic structure of 7 is identical to complex 2; however, THF binding about the terminal coppers (CU-O-THF = 2.394(7) and 2.466(7) angstrom) has introduced the square-pyramidal geometry, indicating that the planar trinuclear complexes 2-6 are coordinatively unsaturated and the terminal metal sites are responsible for further ligations. In the venture of proton-transfer reactions, a successful proton transfer onto the saccharide C-3 alkoxo group has been achieved using 4,6-O-ethylidene-D-glucopyranose, resulting in the self-assembled tetranuclear complex, [Cu-4(HL1)(4)] (8), consisting of the mononuclear Cu(II) chiral building blocks, {Cu(HL1)}., 2006年03月, INORGANIC CHEMISTRY, 45 (5), 2083 - 2092, doi;web_of_science

    研究論文(学術雑誌)

  • Amine mediated proton transfer reaction and C-Cl bond activation of solvent chloroform by a trinuclear copper(II) complex of a glucopyranosylamine derived ligand

    Ajay K. Sah; Tomoaki Tanase

    An amine mediated C-Cl bond activation process of the solvent chloroform has been explored by a coordinatively labile trinuclear Cu(II) complex, [Cu-3(L-1)(2)(MeOH)(H2O)] (1), derived from N-(3-tert-butyl-2-hydroxybenzylidene)-4,6-O-ethylidene-beta-D-glucopyranosylamine (H3L1). The effect of activation is extremely high with methylamine, resulting in the formation of [Cu(MeNH2)(5)]Cl-2 ( 2) and [Cu(L-2)(2)] (3; HL2 = 2-tert-butyl-6-[(methylimino)methyl]phenol), however, under identical conditions it is moderate with ethylamine resulting in the isolation of crystals of the intermediate amine bound trinuclear copper(II) complex, [Cu-3(L-1)(2)(EtNH2)(2)(MeOH)(2)] ( 5), which was further converted into the mononuclear complex, [Cu(HL1)(EtNH2)] ( 6), in a novel crystal- to- crystal transformation. The successive isolation of the ethylamine-bound tri- and mononuclear complexes, 5 and 6, supported the occurrence of proton transfer reactions, which might be a key step in C - Cl bond activation. The primary and secondary amines, 2-aminomethylpyridine, N, N'-dimethylethylenediamine, and 1,4,7-triazacyclononane, also having chelating features further enhance the rate of activation. No activation has been noted in the case of triethylamine and N, N, N', N'-tetramethylethylenediamine. Formation of a carbene- trapped compound, 2,6- xylyl isocyanide, was con. rmed in the reaction of complex 1 with 1,4,7-triazacyclononane and 2,6-xylidine in CHCl3, suggesting that the C-Cl bond cleavage led to the generation of dichlorocarbene. In addition, the mononuclear complex 6 has been transformed into a homotrinuclear complex [Cu-3(L-1)(2)(MeOH)(2)] by treatment with Cu(II) ions in MeOH/ CHCl3, suggesting the possibility that the former could be regarded as a suitable metalloligand for heterotrimetallic complex synthesis., 2006年, DALTON TRANSACTIONS, (31), 3742 - 3751, doi;web_of_science

    研究論文(学術雑誌)

  • Cage-type hexanuclear platinum(0) clusters with diphosphine and isocyanide ligands encapsulating two Mercury(0) atoms

    T Tanase; E Goto; H Takenaka; T Horiuchi; Y Yamamoto; J Kuwabara; K Osakada

    Reduction of a mixture containing [PtCl2(cod)], aromatic isocyanide (RNC; R = 2,6-xylyl (Xyl), 2,4,6-mesityl (Mes)), diphosphine (Ph2P(CH2)(n)PPh2; n = 5 (dpppn), n = 6 (dpphx)), and NH4PF6 by sodium amalgam (< 1%) afforded trigonal-antiprismatic hexanuclear platinum(0) clusters encapsulating two mercury(0) atoms, [Hg2Pt6(mu-RNC)(6)(mu-diphos)(3)] (diphos = dpphx, R = Xyl (6a); diphos = dpppn, R = Xyl (8a), Mes (8b)). Complexes 6a and 8a were characterized by X-ray crystallographic analyses to demonstrate that two triangular platinum(0) units, {Pt-3(mu-RNC)(3)}, are connected by three diphosphine ligands with long methylene chains to form a closed cage of the cluster-based metallocryptand, in which two mercury(0) atoms are incarcerated with a notably short Hg-Hg distance. In complex 8a (n = 5), the centroids of the two Pt(0) triangles are linearly arranged with respect to the Hg-Hg axis to form a pseudo-D-3-symmetrical Hg2Pt6 antiprismatic cluster core (average Pt-Pt = 2.6719 Angstrom, average Pt-Hg = 2.9417 Angstrom, and Hg-Hg = 2.8424(2) Angstrom). In contrast, in complex 6a (n = 6) the two triplatinum planes glide away from the dimercury axis to lose the D-3 symmetry (average Pt-Pt = 2.639 Angstrom, average Pt-Hg = 2.923 Angstrom, and Hg-Hg = 2.826(2) Angstrom). The electronic structures of the Pt3Hg2Pt3 cluster frameworks are discussed on the basis of molecular orbital calculations with EHMO and DFT methods. Hg2Pt6 clusters with an incomplete open-cage structure, [Hg2Pt6(mu-RNC)(6)(RNC)(2)(mu-diphos)(2)] (diphos = dpphx, R Xyl (7a); diphos = dpppn, R = Mes (9b)), were also isolated as minor products and were transformed into the closed-cage clusters 6a and 8b by treatment with an equivalent diphosphine ligand. By using dppb (it = 4), an open-cage mixed-metal cluster with a single mercury atom, [HgPt6(mu-RNC)(6)(RNC)(2)(mu-dppb)(2)] (R = Xyl (10a), Mes (10b)), was obtained as the sole product. When the aliphatic isocyanide t-BuNC was used in the reduction with dpphx, the Hg2Pt6 mixed-metal cluster was not produced, and instead, the PtHgPt trinuclear complex [HgPt2(mu-dpphx)(3)] (11) was obtained in a low yield and was characterized by X-ray crystallography to demonstrate the linear trinuclear structure with a considerable attractive Pt-Hg interaction (average Pt-Hg = 2.7930 Angstrom and Pt-Hg-Pt = 179.591(3)degrees). The electronic structures of 11 are also discussed., 2005年01月, ORGANOMETALLICS, 24 (2), 234 - 244, doi;web_of_science

    研究論文(学術雑誌)

  • Trinuclear coordinatively labile Cu(II) complex of 4,6-O-ethylidene-beta-D-glucopyranosylamine derived Schiff base ligand and its reactivity towards primary alcohols and amines

    AK Sah; MK Tomoaki; T Tanase

    A novel neutral trinuclear Cu(II) complex of a Schiff base ligand derived from D-glucose has been synthesised and structurally characterised, which exhibits excellent alcohol binding affinity and activates the C - Cl bond of chloroform in the presence of primary amine., 2005年, CHEMICAL COMMUNICATIONS, (5), 675 - 677, doi;web_of_science

    研究論文(学術雑誌)

  • Tetranuclear copper(II) complex with glucose-1-phosphate and its phosphate ester exchange with ATP

    M Kato; T Tanase

    The novel tetranuclear copper(II) complexes with alpha-D-glucose-l-phosphates, [CU4(mu-OH)(alpha-D-Glc-1P)(2)(L)(4)(H2O)(2)](NO3)(3) (L = bpy (1), phen (2)), were prepared and characterized by X-ray crystallography. Complex 1 was further transformed into the ATP stabilized tetracopper(II) complex Of [CU4(ATP)(2)(bpy)(4)] (4), where ATP is adenosine 5'-triphosphate., 2005年01月, INORGANIC CHEMISTRY, 44 (1), 8 - 10, doi;web_of_science

    研究論文(学術雑誌)

  • Crystal-to-crystal transformation from tri- to mononuclear Cu(II) complex with a sugar-derived ligand via proton transfer reaction and rearrangement of hydrogen bonding networks

    AK Sah; T Tanase

    Treatment of a glycosylamine derived Cu(II) complex with ethylamine resulted in crystal-to-crystal transformation from trinuclear complex [Cu-3(L-1)(2)(EtNH2)(2)(MeOH)(2)] center dot 2MeOH center dot CHCl3 (2 center dot 2MeOH center dot CHCl3) to a dimeric structure of mononuclear complex [Cu(HL1)(EtNH2)] (3) through proton transfer reaction and rearrangement of hydrogen bonding networks., 2005年, CHEMICAL COMMUNICATIONS, (48), 5980 - 5981, doi;web_of_science

    研究論文(学術雑誌)

  • Reactive rigid-rod organometallic polymers involving linear triplatinum units connected by pi-conjugated bisisocyanides

    T Tanase; E Goto; RA Begum; M Hamaguchi; SZ Zhan; M Iida; K Sakai

    Axial ligand exchange reactions of [Pt-3(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (1) with monoisocyanide molecules afforded a series of linear triplatinum complexes, [Pt-3(mu-dpmp)(2)(RNC)(2)](PF6)(2) (R = 2,4,6-mesityl (2), tert-butyl (4), 4-tolyl (5)) and [Pt-3(mu-dpmp)(2)(XylNC)(t-BuNC)](PF6)(2) (3), which were characterized by spectroscopic, X-ray crystallographic, and absorption (EXAFS) analyses. With the increase of pi-acidity of the terminal isocyanide, the Pt-Pt bond length became longer due to electron transfer from the Pt3 core to the isocyanide group. Terminal ligand exchange reactions of 1 with bulky aromatic bisisocyanides (bisNCn) led to successful isolation of the rigid-rod triplatinum cluster polymers formulated as {[Pt-3(mu-dpmp)(2)(bisNCn)](PF6)(2)}(n) (bisNCn = 2,3,5,6-tetramethylphenylene-1,4-bisisocyanide (bisNC1) (7a), 3,3',5,5'-tetramethylbisphenylene-4,4'-bisisocyanide (bisNC2) (7b)). The structure of compound 7a, determined by X-ray crystallography, was composed of the linear, metal-metal bonded {Pt-3(mu-dpmp)(2)}(2+) fragments (av Pt-Pt = 2.699 Angstrom) covalently connected by the bisisocyanide molecules, resulting in an infinite rigid-rod polymeric structure. By using less bulky bisisocyanides, the ligand exchange reaction stopped at the formation of the triplatinum cluster dimers [(bisNCn)Pt-3(mu-dpmp)(2)(bisNCn)Pt-3(mu-dpmp)(2)(bisNCn)](PF6)(4) (bisNCn = phenylene-1,4-bisisocyanide (bisNC3) (8a), 2,5-dimethylphenylene-1,4-bisisocyanide (bisNC4) (8b)), which were characterized by EXAFS analyses to involve the weakly metal-metal bonded Pt3 fragments (av Pt-Pt = 2.85 Angstrom). The rigid-rod polymer 7a was demonstrated to be quite reactive even in heterogeneous systems toward H+, NO+, tetracyanoethylene (tcne), and electron-deficient alkynes, to afford the cluster polymers formulated as {[Pt-3(mu-H)(mu-dpmp)(2)(bisNC1)](BF4)(3)}(n) (13), {[Pt-3(mu-NO)(2)(mu-dpmp)(2)(bisNC1)](BF4)(4)}(n) (14), {[Pt-3(mu-C12N8)(mu-dpmp)(2)(bisNC1)](PF6)(2)}(n) (15), and {[Pt-3(mu-(RC2R2)-C-1)(mu-dpmp)(2)(bisNC1)](PF6)(2)}(n) (16a, R-1 = H, R-2 = CO2CH3; 16b, R-1 = R-2 = CO2CH3). The structures of the polymers 13-16 were estimated on the basis of the X-ray crystallographic and spectroscopic analyses for the related reference complexes [Pt-3(mu-H)(mu-dpmp)(2)(XylNC)(2)](3+) (9), [Pt-3(mu-NO)(2)(mu-dpmp)(2)(RNC)(2)](BF4)(4) (10, R = Xyl, Mes), [Pt-3(mu-Cl2N8)(mu-dpmp)(2)(RNC)(2)](PF6)(2) (11, R = Xyl, Mes), and [Pt-3(mu-(RC2R2)-C-1)(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (12, R-1 = H or COOCH3, R-2 = COOCH3)., 2004年12月, ORGANOMETALLICS, 23 (25), 5975 - 5988, doi;web_of_science

    研究論文(学術雑誌)

  • Electron-rich diplatinum(0) metallocryptate promoting novel successive encapsulation of acidic hydrides

    E Goto; M Usuki; H Takenaka; K Sakai; T Tanase

    Reaction of [Pt(XyINC)(4)](PF6)(2) with NaBH4 in the presence of 2,7-bis(diphenylphosphino)1,8-naphthyridine (dpnapy) afforded a diplatinum(0) metallocryptate with a tightly encapsulated sodium ion in a pseudo-D-3 helical cage, [Pt2Na(mu-dpnapy)(3)(XylNC)(2)](PF6) (4a; XylNC = 2,6-xylyl isocyanide). The three linear dpnapy ligands in complex 4a are bundled by a sodium ion through six Na-N bonds, and two Pt-0(XyINC) fragments cap each end of the double-tripodal {(dpnapy)(3)Na}(+) unit through three Pt-P bonds. Each electron-rich platinum(O) center adopts a tetrahedral geometry with 18 valence electrons. An analogous dipalladium(0) complex, [Pd2Na(mu-dpnapy)(3)(XylNC)(2)](PF6) (4b), was prepared by reaction of [Pd-3(XylNC)(6)] with dpnapy and NaPF6. The terminal isocyanide ligands of complexes 4a,b were readily replaced by CO (1 atm) to give [M2Na(mu-dpnapy)(3)(CO)(2)](PF6) (M = Pt (4c), Pd (4d)). In the presence of H+ ions, the electron-rich diplatinum metallocryptate 4a interestingly demonstrated successive encapsulation of protons as platinum-bound hydrides, resulting in the formation of [Pt2Na(H)(mu-dpnapy)(3)(XylNC)(2)](PF6)(2) (5) and [Pt2Na(H)(2)(mu-dpnapy)(3)(XylNC)(2)] (PF6)(3) (6). Complexes 5 and 6 were isolated from alternative reactions of [Pt-3(XylNC)(6)] with dpnapy and NaPF6 in the presence of regulated amounts of HPF6. Whereas the structures of 5 and 6 are closely similar to that of 4a, one and two hydrides are trapped into the small room comprised of the {Pt(PCN)(3)Na} framework in complexes 5 and 6, respectively. The hydride attached to the Pt center at the opposite site of isocyanide with the Pt atom deformed slightly toward trigonal-bipyramidal geometry. The structure of 5 is asymmetric with the hydride fixed onto a platinum center, and any site-exchange behavior of the hydride was not observed even in solution. The hydride encapsulation in 5 drags the encountered platinum atom inside by ca. 0.17 Angstrom and causes slight but appreciable distortion around the central Na ion with an average Na-N distance of 2.42 Angstrom for the NO side and 2.54 Angstrom for the PtH side. The structural distortion caused by the hydride encapsulation might have influenced the other Pt center to be less reactive and stabilize the asymmetric structure of 5. Electrochemical measurements for 4a, 5, and 6 were performed to reveal that complex 4a underwent two irreversible one-electron oxidation processes at E-pa(1) = -0.14 V (vs Ag/Ag+) and 0.15 V, corresponding to Pt-2(0) --> (PtPtI)-Pt-0 --> Pt-2(I) with some concomitant structural changes, and the hydride encapsulation made the Pt center redox inactive in 5 and 6, as Pt-0(PtH) --> Pt-I(PtH) (5) and (PtH)(2) were redox silent (6)., 2004年12月, ORGANOMETALLICS, 23 (25), 6042 - 6051, doi;web_of_science

    研究論文(学術雑誌)

  • Formation of thermotropic and lyotropic liquid crystals of bis(N-alkylethylenediamine)silver(I) nitrate

    M Iida; M Inoue; T Tanase; T Takeuchi; M Sugibayashi; K Ohta

    We have synthesized bis(N-hexylethylenediamine)silver(I) nitrate ([Ag(hex-en)(2)]NO3), bis(N-octylethylenediamine)silver(I) nitrate ([Ag(oct-en)(2)]NO3), and bis(N-dodecylethylenediamine)silver(I) nitrate ([Ag(dod-en)(2)]NO3) and investigated the aggregation behavior of [Ag(dod-en)(2)]NO3 and [Ag(oct-en)(2)]NO3 in the liquid state. An X-ray crystallographic analysis revealed that [Ag(dod-en)(2)]NO3 has a dinuclear structure in the crystalline state-the molecular composition unit is [Ag-2(dod-en)(4)](NO3)(2), where the two dod-en ligands bridge two silver ions that are coordinated by four nitrogen atoms. The dinuclear complex is appreciably dissociated into a mononuclear complex in solution. It was found that [Ag(oct-en)(2)]NO3 and [Ag(dod-en)(2)]NO3 form thermotropic liquid crystals in the temperature ranges 48-67 degreesC and 59-96 degreesC, respectively, and a lyotropic liquid crystal was also observed for [Ag(dod-en)(2)]NO3 in n-heptane at around room temperature in the presence of a small amount of water. The structures of the thermotropic and lyotropic liquid crystals of [Ag(dod-en)(2)]NO3 were identified as a typical smectic A (S-A) type and a nematic one, respectively. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004., 2004年10月, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (19), 3920 - 3929, doi;web_of_science

    研究論文(学術雑誌)

  • Bis[m-3-(Nユ-methyl-4,4ユ-bipyridinium-1-yl)propionamidato]bis[cis-diammineplatinum(II)] Hexaperchlorate Dihydrate: A Head-to-tail Isomer

    K Sakai; Y Yokoyama; H Hama; K Kato; Y Ikuta; T Tsubomura; T Tanase

    In the title compound, [Pt-2(mu-C14H16N3O)(2)(NH3)(4)](ClO4)(6).-2H(2)O, the diplatinum(II) cation is found to be a head-to-tail isomer. The intradimer Pt-Pt distance [3.0304 (7) Angstrom] is much shorter than the value of 3.0852 (13) Angstrom reported for the analogous cis-diammineplatinum(II) dimer bridged by 2-(N'-methyl-4,4'-bipyridinium-1-yl)acetamidates [Sakai, Ikuta, Tsubomura, Kato, Yokoyama, Kajiwara & Ito (2003). Acta Cryst. E59, m780-m783], showing that the electron density at the metal centers is higher in the title system than in the previously reported system. The shortest interdimer Pt...Pt distance is 8.4585 (8) Angstrom., 2004年05月, ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 60, M664 - M667, doi;web_of_science

    研究論文(学術雑誌)

  • Novel crystal structure and mesomorphism appeared in oxovanadium(IV) salen complexes with 4-substituted long alkoxy chains

    Y Abe; K Nakabayashi; N Matsukawa; M Iida; T Tanase; M Sugibayashia; K Ohta

    A series of V(IV) complexes with 4-substituted salen ligands, formulated as [VO((4-CnH2n+1O)(2)salen)] (n = 12 (1), 14 (2), 16 (3), 18 (4), and 20 (5)), which formed a novel biomembrane-like bilayer crystal structure, exhibited an unprecedented bilayer mesophase having symmetry Pa2(1) in the layers. (C) 2004 Elsevier B.V. All rights reserved., 2004年04月, INORGANIC CHEMISTRY COMMUNICATIONS, 7 (4), 580 - 583, doi;web_of_science

    研究論文(学術雑誌)

  • Linear, redox-active Pt-6 and Pt2Pd2Pt2 clusters

    E Goto; RA Begum; SZ Zhan; T Tanase; K Tanigaki; K Sakai

    2004年, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 43 (38), 5029 - 5032, doi;web_of_science

    研究論文(学術雑誌)

  • An azonia derivative of hexahelicene

    K Sato; S Arai; T Yamagishi; T Tanase

    In 8a-azonia[6]helicene hexafluorophosphate or 8a-azoniaphenanthro[3,4-c]phenanthrene hexafluorophosphate, C25H16N+.PF6- , replacement of an outer bridgehead carbon of hexahelicene by a quaternary Nsp(2) atom results in a geometrical change in the helical structure. The racemic heterohelicene forms homochiral columnar stacks through intermolecular pi-pi donor-acceptor interactions in the crystalline state., 2003年03月, ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 59, O162 - O164, doi;web_of_science

    研究論文(学術雑誌)

  • Recent development of linearly ordered multinuclear transition-metal complexes

    T Tanase

    This paper reviews the recent development of linearly ordered multinuclear transition-metal complexes, which have been of increasing interest as potential nanostructured molecular units and their precursors. In particular, it focuses on our recent results of platinum-based homo- and heteromultimetallic complexes supported by the tridentate phosphine ligands, bis(diphenylphosphinomethyl)phenylphosphine (dpmp). The synthetic strategy involved the metal core expansion using the diplatinum precursors having two uncoordinated phosphine pendants, syn- and anti-[Pt-2(mu-dpmp)(2)(RNC)(2)](2+) (11 and 12), which allowed us to gain access to versatile homo- and heterotrinuclear complexes with Pt2M cores. Reactions of 11 with d(10) and d(8) metal fragments afforded the Pt-Pt-M metal frameworks (M = Pt, Pd, Au, Ag, Cu, Ir, Rh), and in contrast, those of 12 gave the Pt-M-Pt ones (M = Pt, Pd, Rh). The inserted position of the additional metal interestingly depends on the two dpmp arrangement of the starting diplatinum complexes. The corresponding chemistry of palladium and gold complexes is also described. Since the metal-metal bonded triplatinum complex, linear-[Pt-3(mu-dpmp)(2)(RNC)(2)](PF6)(2) (16), was regarded as a minimal model for the surface of metal catalysts, its reactions with various small organic molecules were examined. Further, the axial ligand exchange reactions of 16 with bulky aromatic bisisocyanide led to a one-dimensional assemblage of the linear Pt3 units, resulting in rigid rod-like cluster polymers, and the reduction of 16 afforded the linearly ordered hexaplatinum cluster molecules supported by four dpmp ligands through a direct combination of the two linear Pt-3 fragments., 2002年07月, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 75 (7), 1407 - 1422, web_of_science

  • Unprecedented sugar-dependent in vivo antitumor activity of carbohydrate-pendant cis-diamminedichloroplatinum(II) complexes

    Yuji Mikata; Yoshie Shinohara; Kazumi Yoneda; Yuka Nakamura; Izabela Brudziska; Tomoaki Tanase; Takashi Kitayama; Rie Takagi; Tadashi Okamoto; Isamu Kinoshita; Matsumi Doe; Chris Orvig; Shigenobu Yano

    Eight carbohydrate-pendant platinum(II) complexes have been synthesized from carbohydrate-diamine conjugates. D-Glucose, D-mannose, D-galactose, D-xylose, and L-glucose are attached to the dichloroplatinum(II) moiety by 1,3- or 1,2-diaminopropane chelates through with an O-glycoside bond. All the carbohydrate moieties reduced the toxicity inherent with platinum(II) complexes. © 2001 Elsevier Science Ltd. All rights reserved., 2001年12月03日, Bioorganic and Medicinal Chemistry Letters, 11 (23), 3045 - 3047, doi;pubmed;scopus;scopus_citedby

    研究論文(学術雑誌)

  • Substrate-dependent chemoselective aldose-aldose and aldose-ketose isomerizations of carbohydrates promoted by a combination of calcium ion and monoamines

    T Tanase; T Takei; M Hidai; S Yano

    Epimerization of aldoses at C-2 has been extensively investigated by using various metal ions in conjunction with diamines, monoamines, and aminoalcohols. Aldoses are epimerized at C-2 by a combination of alkaline-earth or rare-earth metal ions (Ca2+, Sr2+, pr(3+), or Ce3+) and such monoamines as triethylamine. In particular, the Ca2+-triethylamine system proved effective in promoting aldose-ketose isomerization as well as C-2 epimerization of aldoses. C-13 NMR studies using D-(1-C-13)glucose and D-(1-C-13)galactose with the CaCl2 system in CD3OD revealed that the C-2 epimerization proceeds via stereospecific rearrangement of the carbon skeleton, or 1,2-carbon shift, and ketose formation proceeds partially through an intramolecular hydrogen migration or 1,2-hydride shift and, in part, via an enediol intermediate. These simultaneous aldose-aldose and aldose-ketose isomerizations showed interesting substrate-dependent chemoselectivity. Whereas the mannose-type aldoses having 2,3-erythro configuration (D-mannose, D-lyxose, and D-ribose) showed considerable resistance to both the C-2 epimerization and the aldose-ketose isomerization, the glucose-type sugars having 2,3-threo and 3,4-threo configurations, D-glucose and D-xylose, are mainly epimerized at C-2 and those having the 2,3-threo and 3,4-erythro configurations, D-galactose and D-arabinose, were mostly isomerized into 2-ketoses. These features are of potential interest in relevance to biomimic sugar transformations by metal ions. (C) 2001 Elsevier Science Ltd. All rights reserved., 2001年07月, CARBOHYDRATE RESEARCH, 333 (4), 303 - 312, web_of_science

    研究論文(学術雑誌)

  • Trinuclear Zn(II) and Cu(II) homo and heterotrimetallic complexes involving D-glucopyranosyl and biscarboxylate bridging ligands. A substrate binding model of xylose isomerases

    T Tanase; H Inukai; T Onaka; M Kato; S Yano; SJ Lippard

    Reactions of MCl2. nH(2)O with N,N ' -bis(D-glucopyranosyl)-1,4,7-triazacyclononane ((D-Glc)(2)-tacn), which was formed from D-glucose and 1,4,7-triazacyclononane (tacn) in situ, afforded a series of mononuclear divalent metal complexes with two beta -D-glucopyranosyl moieties, [M{(D-Glc)(2)-tacn}Cl]Cl (M = Zn (11), Cu (12), Ni (13), Co(14)). Complexes 11-14 were characterized by analytical and spectroscopic measurements and X-ray crystallography and were found to have a distorted octahedral M(II) center ligated by the pentacoordinate N-glycoside ligand, (beta -D-glucopyranosyl)(2)-tacn, and a chloride anion. Each D-glucose moiety is tethered to the metal center through the beta -N-glycosidic bond with tacn and additionally coordinated via the C-2 hydroxyl group, resulting in a A-gauche five-membered chelate ring. When L-rhamnose (6-deoxy-L-mannose) was used instead Of D-glucose, the nickel(II) complex with two beta -L-rhamnopyranosyl moieties, [Ni{(D-Man)(2)-tacn}(MeOH)]Cl-2 (15), was obtained and characterized by an X-ray analysis. Reactions of 11 (M = Zn) with [Zn(XDK)(H2O)] (21) or [Cu(XDK)(PY)(2)] (22) (H2XDK = m-xylylenediamine bis(Kemp's triacid imide)) yielded homo, and heterotrimetallic complexes formulated as [Zn2M '{(D-Glc)2-tacn}(2)(XDK)]Cl-2 (M ' = Zn (31), Cu (32)). The similar reactions of 12 (M = Cu) with complex 21 or 22 afforded [Cu2M '{(D-Glc)(2)-tacn}(2)(XDK)]Cl-2 (M ' = Cu (33), Zn (34)). An X-ray crystallographic study revealed that complexes 31 and 34 have either Zn-3(II) or (CuZnCuII)-Zn-II-Cu-II trimetallic centers bridged by two carboxylate groups of XDK and two D-glucopyranosyl residues. The (MM)-M-... ' separations are 3.418(3)-3.462(3) Angstrom (31) and 3.414(1)-3.460(1) Angstrom (34), and the (MM)-M-... ' M-... angles are 155.18(8)degrees (31) and 161.56(6)degrees (34). The terminal metal ions are octahedrally coordinated by the (D-Glc)2-tacn ligand through three nitrogen atoms of tacn, two oxygen atoms of the C-2 hydroxyl groups of the carbohydrates, and a carboxylate oxygen atom of XDK ligand. The central metal ions sit in. a distorted octahedral environment ligated by four oxygen atoms of the carbohydrate residues in the (D-Glc)2-tacn ligands and two carboxylate oxygen atoms of XDK. The deprotonated beta -D-glucopyranosyl unit at the C-2 hydroxyl group bridges the terminal and central ions with the C-2 mu -alkoxo group, with the C-1 N-glycosidic amino and the C-3 hydroxyl groups coordinating to each metal center. Complexes 31-34 are the first examples of metal complexes in which D-glucose units act as bridging ligands. These structures could be very useful substrate binding models of xylose or glucose isomerases, which promote D-glucose D-fructose isomerization by using divalent dimetallic centers bridged by a glutamate residue., 2001年07月, INORGANIC CHEMISTRY, 40 (16), 3943 - 3953, doi;web_of_science

    研究論文(学術雑誌)

  • Sugar-pendant diamines

    Y Mikata; Y Shinohara; K Yoneda; Y Nakamura; K Esaki; M Tanahashi; Brudzinska, I; S Hirohara; M Yokoyama; K Mogami; T Tanase; T Kitayama; K Takashiba; K Nabeshima; R Takagi; M Takatani; T Okamoto; Kinoshita, I; M Doe; A Hamazawa; M Morita; F Nishida; T Sakakibara; C Orvig; S Yano

    A set of 1,3-propanediamine derivatives connected to carbohydrates (5) has been prepared in four steps from peracetylated sugar and 1,3-dibromo-2-propanol in 60-73% yields. D-Glucose, D-mannose, D-galactose, D-xylose, D-ribose, and maltose are utilized as sugar molecules in this work. The diamine moiety was connected to the C1 carbon of the glycopyranose ring via an O-glycoside bond. All of the anomeric configurations and sugar puckering conformations, except in the D-maltose derivative, were determined by X-ray crystallography of the diazido or dibromo precursors. While glycosidation of peracetylated galactopyranose with 1,3-dibromo-2-propanol in the presence of boron trifluoride afforded both anomers, the neighboring group participation of the 2-acetoxy group yielded a single anomer for the other substrates. This method has been used to synthesize a library of sugar-pendant diamines including an OH-protected derivative (6), and an N,N ' -diisopropyl-substituted derivative (7). A similar series of reactions using 2,3-dibromo-1-propanol gave ethylenediamine-type derivatives (11), and bis(bromomethyl)bis(hydroxymethyl)methane (12) gave bisglucose-pendant derivatives (16)., 2001年06月, JOURNAL OF ORGANIC CHEMISTRY, 66 (11), 3783 - 3789, doi;web_of_science

    研究論文(学術雑誌)

  • Cyclic dimerization of tetracyanoethylene promoted on linear triplatinum centres leading to novel nitrene-bridged Pt-3 complexes

    T Tanase; M Hamaguchi; RA Begum; E Goto

    Reactions of linear triplatinum complexes, linear-[Pt-3(mu -dpmp)(2)(RNC)(2])(PF6)(2) (1), with excess tetracyanoethylene (tcne) afford the novel nitrene-bridged asymmetrical A-frame triplatinum complexes, [Pt-3(mu -dpmp)(2)(mu -C12N8)(RNC)(2)](PF6)(2) (2a: R = 2,6-xylyl; 2b: R = 2,4,6-mesityl, dpmp = bis(diphenylphosphinomethyl)phenylphosphine) in which two tcne molecules are coupled to form a (heptacyanocyclopent-1-enyl)nitrene moiety., 2001年06月, CHEMICAL COMMUNICATIONS, (12), 1072 - 1073, web_of_science

    研究論文(学術雑誌)

  • Linearly ordered Pt2Rh and Pt2Ir heterotrinuclear complexes bridged by tridentate phosphine ligands

    T Tanase; RA Begum; H Toda; Y Yamamoto

    Reactions of the diplatinum complex supported by two tridentate phosphine ligands, syn[Pt-2(mu -dpmp)(2)L-2] (PF6)(2) (1), with [MCl(cod)](2) (M = Rh, Ir) afforded the linearly ordered Pt-Pt-M clusters [Pt-2{MClL}(mu -dpmp)(2)L](PF6)(2) (6a, M = Rh; 6b, M = Ir) and the asymmetrical A-frame clusters [Pt-2{M(mu -Cl)L}(mu -dpmp)(2)L](PF6)(2) (7a, M = Rh; 7b, M = Ir), where dpmp = bis(diphenylphosphinomethyl)phenyphosphine and L = 2,6-xylyl isocyanide (XylNC). Complexes 6 involve a linear Pt2M trinuclear core supported by two dpmp ligands. The three metals are joined by two metal-metal bonds, where the Pt-Pt and Pt-M bonds can be viewed, respectively, as a d(9)-d(9) covalent and a d(9)<--d(8) dative interactions. Complexes 7 consists of an asymmetrical Pt-2(<mu>-Cl)M A-frame structure. Reaction of 6a with 1 equiv of L (= XylNC) yielded [Pt-2{RhClL2}(mu -dpmp)(2)L](PF6)(2) (8a), and that with excess L led to [Pt-2{RhL3}(mu -dpmp)(2)L] (PF6)(3) (9a). The additional isocyanide molecules are attached exclusively to the Rh center. Complex 6a by treatment with CO was readily converted into an CO adduct, [Pt-2(RhClL(mu -CO)}(mu -dpmp)(2)L] (PF6)(2) (10a), which easily regenerated 6a with dinitrogen passed through its solution. The structure of 10a was determined by X-ray analysis to show that a carbon monoxide molecule was added to the Pt-Rh bond (2.762(2) Angstrom), resulting in an asymmetrical CO bridging structure. The similar reaction of 7a with CO yielded another kind of CO adduct, [Pt-2{Rh(mu -Cl)(mu -CO)L}(mu -dpmp)(2)L](PF6)(2) (11a), which did not regenerate the starting complex 7a. Reaction of 6a with an electron-deficient alkyne, HC=CCO2Me, led to the alkyne-inserted compound [Pt(mu -HC=CCO2Me)Pt{RhClL},{mu -dpmp)(2)L](PF6)(2) (12a), in which the alkyne is site-selectively inserted into the Pt-Pt bond. The present results suggested that the Rh center has an electrophilic property and the Pt-2 unit has a nucleophilic one in the linear Pt2Rh structure., 2001年03月, ORGANOMETALLICS, 20 (5), 968 - 979, doi;web_of_science

    研究論文(学術雑誌)

  • Quinolizinium hexafluorophosphate

    K Sato; S Arai; T Yamagishi; T Tanase

    The crystal structure of the title compound, C9H8N+. PF6-, was measured at 145 K. The cationic part of the compound has crystallographically imposed 2/m symmetry with N/C disorder., 2001年02月, ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 57, 174 - 175, web_of_science

    研究論文(学術雑誌)

  • Unsymmetrical A-frame Pt2Pd trinuclear complexes: Site-selective apparent double insertion of alkynes into Pd-Pt and Pd-P bonds

    T Tanase; RA Begum

    Reactions of the linearly ordered Pt2Pd mixed-metal complex linear-[Pt2Pd(mu -dpmp)(2)(XylNC)(2)](PFs)2 (1b) (dpmp = bis(diphenylphosphinomethyl)phenylphosphine XylNC = 2,6-xylyl isocyanide), with electron-deficient alkynes, RC drop CR', led to the formation of a series of unsymmetrical A-frame clusters formulated as [Pt2Pd(mu -dpmp)(mu -Ph2PCH2P(Ph)CH2P(Ph)(2)CRCR')(XylNC)(2)](PF6)(2) (R = R' = CO2Me (2); R = R' = CO2Et (3); R = H, R' = CO2Me (4); R = H, R' = CO2Et (5); R = CH3, R' = CO2Et (6)) in considerable yields, in which the alkyne molecule was site-selectively inserted into the Pt-Pd bond and was further reacted with a phosphine unit of a dpmp ligand through double bond breaking of the C dropC unit. Complexes 2-6 were characterized by IR, electronic absorption, and NMR spectroscopic techniques and X-ray crystallography (2, 4, and 5) to reveal that the apparent double insertion of the acetylene unit takes place site-selectively on the Pt-Pd-P heterometallic center. In complexes 4 and 5, the P-C bond formation occurred regioselectively between the terminal alkyne carbon and phosphine unit of dpmp, resulting in a mu-eta (1):eta (2)-phosphorus C-2 ylide bridging structure. The reaction mechanism was discussed. In contrast, reaction of Ib with excess HBF4 afforded [Pt2Pd(mu -H)(dpmp)(2)(XylNC)(2)] (BF4)(3) (8), where a proton was oxidatively added to the Pt-Pt bond vs the Pt-Pd bond. From the X-ray crystal structure of 8, the structural change accompanied by the addition was revealed to be fairly small, with a slight elongation of the Pt-Pt bond from 2.690(1) Angstrom (1b) to 2.867(2) Angstrom (8). These results demonstrated that the heterometal (Pd) was able to alter the reactivity of the linear trimetallic clusters and interestingly regulated its specificity., 2001年01月, ORGANOMETALLICS, 20 (1), 106 - 114, doi;web_of_science

    研究論文(学術雑誌)

  • Insertion of strongly electron withdrawing cyanoolefins into the C-H bond in pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) complexes containing P-O or P-O-O ' coordinations

    Y Yamamoto; XH Han; S Nishimura; K Sugawara; N Nezu; T Tanase

    Complexes Cp*MCl(MDMPP-P, O) (1a: M = Rh, 1b: M = Ir; eta (5)-C5Me5; MDMPP-P,O = PPh2(C6H3-2-O-6-MeO)) readily react with tcne or tcnq to form the 1:1 adducts [Cp*MCl(MDMPP-P, O)(ol)] (ol = tcne (c), tcnq (d)) (3ac: M = Rh, ol = tcne; 3bc: M = Ir, ol = tcne; 4ad: M = Rh, ol = tcnq; 4bd: M = Ir, ol = tcnq), derived from insertion of cyanoolefins into the C-H bond adjacent to the metal-O bond. Complex Cp*Ir(TDMPPP,O,O') 2b (TDMPP-P,O,O' = P{C6H3-2,6-(MeO)(2)}(C6H3-2-O-6-MeO)(2)) bearing a (P,O,O') coordination was treated with 1 equiv of tcne, tcnq, or Me-2-tcnq (e) to give the products in which one molecule of cyanoolefin was inserted, [Cp*Ir(TDMPP-P, O, O')(ol)] (5bc: ol = tcne; 6bd: ol = tcnq; 6be: ol = Me-2-tcnq). Reactions with 2 equiv of cyanoolefin gave the products [Cp*Ir(TDMPP-P,O, O')(ol)(2)] (7bc: ol = tcne; 8bd: ol = tcnq), in which insertion occurred at two C-H positions adjacent to the Ir-O bonds. Structural data for 3ac, 3bc, 4ad, 5bc, and 7bc are described., 2001年01月, ORGANOMETALLICS, 20 (2), 266 - 272, doi;web_of_science

    研究論文(学術雑誌)

  • Diruthenium complexes with hydrotris(1-pyrazolyl)borate face-capping ligands involving {Ru-2(mu-O or mu-OH)(mu-carboxylato)(2)} cores

    T Tanase; N Takeshita; C Inoue; M Kato; S Yano; K Sato

    Reactions of [Ru-2(RCOO)(4)Cl] (R=Me, Ph) with K[HBpz(3)] (HBpz(3)(-)=hydrotris(1-pyrazolyl)borate) afforded the oxo-bridged diruthenium(III) complexes, [Ru-2(mu -O)(mu -RCOO)(2)(HBpz(3))(2)] (R=Me (1a), Ph (1b)) in moderate yields. Complexes 1 were converted by treatment with HPF6 into the hydroxo-bridged diruthenium(III) complexes, [Ru-2(mu -OH)(mu -RCOO)(2)(HBpz(3))(2)](PF6) (R=Me (2a), Ph (2b)), and by reaction with (NH4)(2)Ce(NO3)(6), to the oxo-bridged mixed-valence diruthenium(III, IV) complexes, [Ru-2(mu -O)(mu -RCOO)(2)(HBpz(3))(2)](PF6) (R=Me (3a), Ph (3b)). Complexes 1-3 were characterized by elemental analysis, IR, UV-Vis, and H-1 NMR spectroscopies, and X-ray absorption and crystallographic analyses (1a and 2a). Complex 1a consists of a {Ru-2(mu -oxo)(mu -carboxylato)(2)} core with two terminal face-capping HBpz(3)(-) ligands (Ru . . . Ru=3.2544(7) Angstrom). Protonation of the mu -oxo group of 1a expanded the Ru . . . Ru distance to 3.4490(9) Angstrom, which was elucidated by X-ray crystallography, and one-electron oxidation of 1a also increases this length to 3.38 Angstrom, determined by EXAFS analysis. These complexes interestingly showed, in cyclic voltammograms, a wide range of redox processes, [Ru-2(II)]<----> [(RuRuIII)-Ru-II]<----> [Ru-2(III)]<----> [(RuRuIV)-Ru-III]<----> [Ru-2(IV)], which are coupled with protonation/deprotonation at the monoatom bridge. When complex 1b was reduced with sodium amalgam, the mononuclear ruthenium(II) complex [Ru(PhCOO)(HBpz(3))(CH3CN)(2)] (4b) was isolated and characterized by spectroscopic techniques and EXAFS analysis. Upon exposure to air or dioxygen, complex 4b readily regenerated the oxo-bridged dimer 1b, and the oxo atom was confirmed to be derived from dioxygen by an isotopically-labeled experiment. The present results demonstrate the versatile redox states of diruthenium centres terminally capped by HBpz(3)(-) ligands., 2001年, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (15), 2293 - 2302, doi;web_of_science

    研究論文(学術雑誌)

  • Preparation and characterization of palladium and platinum complexes bearing 1,8-bis[(diphenylphsphino)methyl]naphthalene

    Y Yamamoto; Y Fukui; K Matsubara; H Takeshma; F Miyauchi; T Tanase; G Yamamoto

    Reaction of MCl2(cod) (M=Pd, Pt) with 1,8-bis[(diphenylphosphino)methyl]napgthalene (1,8-dpmn) gave MCl2(1,8-dpmn) 1 (M=Pd), 2(M=Pt) as confirmed by X-ray analyses. Complex 1 reacted with ylyl isocyanide a (XyINC) in the presence of NaPF6 to give [Pd(1,8-dpmn)(XyINC)(2)](PF6)(2) 3a. Reactions of dinuclear complexes [M-2(RNC6)(6)](PF6)(2) (4: M=Pd, 5: M=Pt; R=Xyl(a) or 2,4,6-Me2C6H2 (b) (Mes)) with one or two equiv. of 1,8-dpmn gave [M-2(1,8-dpmn)(RNC)(4)](PF6)(2) 6(M=Pd) and 7 (M=Pt), or [M-2(1,8-dpmn)(2)(RNC)(2)](PF6)(2) 8 (M=Pd) and 9 (M=Pt). The structure of 6b, 7b and 8b were confirmed by X-ray analyses. Reaction of [Pd2Cl2(XyINC)(4) with two equiv. of 1,8-dpmn in the presence of NaPF6 gave 8a, whereas the reaction in the presence of NH4PF6 produced 10a together with 7a. It was confirmed by and X-ray analysis of 10a that the crystal lattice is constructed by two types of cations (3a and two 2,2,6,6-tetramethyl-4-piperidonium) and four PF6 anions. Photochemical reaction of 6a and 8a in CH2Cl2 led to cleavage of the Pd-Pd bond, giving [PdCl(XyINC)(3)](PF6) and [PdCl(1,8-dpmn)(XyINC)(PF6)., 2001年, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (11), 1773 - 1781, web_of_science

    研究論文(学術雑誌)

  • Hydrophilic-hydrophobic balance of bis(octylethylenediamine) Zn(II), Cd(II), and Pd(II) chlorides in methanol/water and chloroform/water systems

    M Iida; H Er; N Hisamatsu; T Tanase

    Double-chained bis(N-octylethylenediamine ( = OE)) complexes, such as Zn(OE)(2)Cl-2, Cd(OE)(2)Cl-2 and Pd(OE)(2)Cl-2, were prepared and their selective solubilities in water/chloroform and water/methanol solutions were studied. Although all the complexes are poorly soluble in water, they showed clearly different solubilities in the water/organic mixed solvents depending on each amphiphilic character., 2000年05月, CHEMISTRY LETTERS, (5), 518 - 519, web_of_science

    研究論文(学術雑誌)

  • Synthesis and characterization of gold(I) complexes with a triphosphine ligand having a bent trinuclear core interacted with a halide anion

    T Tanase; K Masuda; J Matsuo; M Hamaguchi; RA Begum; S Yano

    The reaction of [AuCl(PPh3)] with bis(diphenylphosphinomethyl)phenylphosphine (dpmp) in a 3:2 ratio in the presence of NH4PF6 afforded the trinuclear gold(I) complex, [Au-3(mu-dpmp)(2)Cl](PF6)(2) (6), in good yield. Complex 6 was readily transformed, by treatment with 1 equiv. of KX (X = Br, I) in a methanol/dichloromethane mixed solvent, into the analogous complexes [Au-3(mu-dpmp)(2)X](PF6)(2) (X = Br (7), I (8)). Complexes 6-8 were characterized by elemental analysis, IR, P-31{H-1} NMR, and W-Vis absorption spectroscopic techniques and X-ray crystallographic analysis. Complexes 6-8 consist of three Au(I) ions bridged by two dpmp ligands (av. Au-Au = 2.944 Angstrom (6), 2.950 Angstrom (7), 2.934 Angstrom (8)), which further interacted with a halide anion leading to a bent trinuclear core with Au-Au-Au angles 143.46(4)degrees (6), 141.12(6)degrees (7), and 142.73(5)degrees (8). The bent trimetallic core is assumed to be retained even in solution on the basis of their spectral data. and in particular, emission spectra were entirely different depending on the halide anion; complexes 6 (X = Cl) and 8 (X = I) were luminescent with emission band maxima at 469 and 551 nm. respectively, whereas complex 7 (X = Br) was not luminescent. The present results demonstrated that the structures and properties of dpmp-bridged trigold(I) complexes were dramatically influenced by the halide anions used. (C) 2000 Elsevier Science S.A. All rights reserved., 2000年02月, INORGANICA CHIMICA ACTA, 299 (1), 91 - 99, web_of_science

    研究論文(学術雑誌)

  • Novel (MnMnMnII)-Mn-II-Mn-III trinuclear complexes with carbohydrate bridges derived from seven-coordinate manganese(II) complexes with N-glycoside

    T Tanase; S Tamakoshi; M Doi; M Mikuriya; H Sakurai; S Yano

    Reactions of MnX2. nH(2)O with tris(N-(D-mannosyl)-2-aminoethyl)amine ((D-Man)(3)-tren), which was formed from D-mannose and tris(2-aminoethyl)amine (tren) in situ, afforded colorless crystals of [Mn((D-Man)(3)-tren)]X-2 (3a, X = Cl; 3b, X = Br; 3c, X = NO3; 3d, X = 1/2SO(4)). The similar reaction of MnSO4. 5H(2)O with tris(N-(L-rhamnosyl)-2-aminoethyl)amine ((L-Rha)(3)-tren) gave [Mn((L-Rha)(3)-tren)]SO4 (4d), where L-rhamnose is 6-deoxy-L-mannose. The structures of 3b and 4d were determined by X-ray crystallography to have a seven-coordinate Mn(II) center ligated by the N-glycoside ligand, (aldose)(3)-tren, with a C-3 helical structure. Three D-mannosyl residues of 3b are arranged in a Delta(ob(3)) configuration around the metal, leading to formation of a cage-type sugar domain in which a water molecule is trapped. in 4d, three L-rhamnosyl moieties are in a Delta(lel(3)) configuration to form a facially opened sugar domain on which a sulfate anion is capping through hydrogen bonding. These structures demonstrated that a configurational switch around the seven-coordinate manganese(II) center occurs depending on its counteranion. Reactions of 3a, 3b, and 4d with 0.5 equiv of Mn(II) salt in the presence of triethylamine yielded reddish orange crystals formulated as [{Mn((aldose)(3)-tren)}(2)Mn(H2O)]X-3. nH(2)O (5a, aldose = D-Man, X = Cl: 5b, aldose = D-Man, X = Br; 6d, aldose = L-Rha, X = 1/2SO(4)). The analogous trinuclear complexes 6a (aldose = L-Rha, X = Cl), 6b (aldose = L-Rha, X = Br), and 6c (aldose = L-Rha, X = NO3) were prepared by the one-pot reaction of Mn(II) salts with (L-Rha)(3)-tren without isolation of the intermediate Mn(II) complexes. X-ray crystallographic studies revealed that 5a, 5b, 6c, and 6d have a linearly ordered trimanganese core, (MnMnMnII)-Mn-II-Mn-III, bridged by two carbohydrate residues with Mn-Mn separations of 3.845(2)-3.919(4) Angstrom and Mn-Mn-Mn angles of 170.7(1)-173.81(7)degrees. The terminal Mn(II) atoms are seven-coordinate with a distorted mono-face-capped octahedral geometry ligated by the (aldose)(3)-tren ligand through three oxygen atoms of C-2 hydroxyl groups, three N-glycosidic nitrogen atoms, and a tertiary amino group. The central Mn(III) atoms are five-coordinate ligated by four oxygen atoms of carbohydrate residues in the (aldose)(3)-tren ligands and one water molecule, resulting in a square-pyramidal geometry. In the bridging part, a beta-aldopyranosyl unit with a chair conformation bridges the two (MnMnIII)-Mn-II ions with the C-2 mu-alkoxo group and with the C-1 N-glycosidic amino and the C-3 alkoxo groups coordinating to each metal center. These structures could be very useful information in relation to xylose isomerases which promote aldose-ketose isomerization by using divalent dimetal centers such as Mn2+, Mg2+, and Co2+., 2000年02月, INORGANIC CHEMISTRY, 39 (4), 692 - 704, web_of_science

    研究論文(学術雑誌)

  • Tetranuclear iron(III) complexes with a planar (mu-oxo) (mu-hydroxo)bis(mu-alkoxo)bis(mu-carboxylato)tetrairon core derived from hydrolysis of carboxylic acid amides by diiron(III) center

    T Tanase; C Inoue; E Ota; S Yano; M Takahashi; M Takeda

    Reactions of Fe(NO3)(3). 9H(2)O with 0.5 equiv. of 2-hydroxy-1,3-diaminopropane N,N,N',N'-tetraacetic acid (H(5)dhpta) in a mixed solvent of water and N,N-dimethyl carboxylic acid amide (N,N-Me2NCOR; R = H, CH3, CH2CH3) at 105 degrees C for 22 h gave pale green crystals formulated as (Me2NH2)(4)[Fe-4(dhpta)(2)(mu-O)(mu-OH)(O2CR)(2)](NO3) (R = H (1a), CH3 (1b), CH2CH3 (1c)) in good yields. Complexes 1a-c could also be prepared from reaction of Fe(NO3)(3). 9H(2)O with H(5)dhpta in the presence of the corresponding carboxylic acid (RCO2H; R = H, CH3, CH2CH3) at room temperature with the pH adjusted to about 5 by Me2NH. The tetrairon(III) complexes were characterized by elemental analyses, IR, electronic absorption, the Fe-57 Mossbauer spectrum, and X-ray crystallographic analyses to comprise a planar (mu-oxo)(mu-hydroxo)bis(mu-alkoxo)bis(mu-carboxylato)tetrairon(III) cluster core bridged by two dhpta and two carboxylate ligands. The central two oxo groups are protonated to form a strongly hydrogen bonded (O-H-O)(3-) bridge. The Fe-57 Mossbauer spectrum for Ib clearly demonstrated that the four iron sites are equivalent as a high-spin octahedral iron(III) state. When Fe(NO3)(3). 9H(2)O was treated with H(5)dhpta (0.5 equiv.) and RCO2H (R = CH3, CH2OH) in N,N-dimethylformamide (dmf) in the absence of Me,NH, diiron(III) complexes bridged by a dhpta and a carboxylate ligand, [Fe-2(dhpta)(mu-O2CR)(dmf)(2)] (R=CH3 (2b), CH2OH (2d)), were obtained in good yields. Complex 2b was further converted to the tetranuclear complex Ib by treatment with Me,NH. These results strongly indicated that amide hydrolysis took place on the dimetal center at an initial step to give the diiron(III) complex with a carboxylate bridge which was subsequently converted into the tetrairon(III) complex. (C) 2000 Elsevier Science S.A. All rights reserved., 2000年01月, INORGANICA CHIMICA ACTA, 297 (1-2), 18 - 26, web_of_science

    研究論文(学術雑誌)

  • A triangular triplatinum complex with electron-releasing SiPh2 and PMe3 ligands: [{Pt(mu-SiPh2)(PMe3)}(3)]

    K Osakada; M Tanabe; T Tanase

    2000年, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 39 (22), 4053 - 4055, web_of_science

    研究論文(学術雑誌)

  • Feasible attachment of a dinuclear ruthenium complex to gold electrode surfaces. A screening method to find functional electrodes

    H Takagi; A Ichimura; T Yano; Kinoshita, I; K Isobe; M Abe; Y Sasaki; Y Mikata; T Tanase; N Takeshita; C Inoue; Y Kimura; S Endo; K Tamura; S Yano

    A dinuclear ruthenium complex [Ru-2(dhpta)(mu-O2CCH3)(2)](-) (H(s)dhpta = 1,3-diamino-2-hydroxypropane-N,N,N', N'-tetraacetic acid) is accumulated on a gold surface by using the ligand substitution reaction of bridging acetate in the complex by terminal benzoate in a self-assembled monolayer with 4-(6-mercaptohexoxy)benzoic acid. The accumulated complex, which shows a surface redox couple corresponding to (RuRuIII)-Ru-III/(RuRuII)-Ru-III, covers the gold surface completely. The ligand substitution reaction is applicable for the accumulation of other complexes and useful for the designing of functional electrodes., 1999年12月, ELECTROCHEMISTRY, 67 (12), 1192 - 1193, web_of_science

    研究論文(学術雑誌)

  • Synthesis and characterization of photosensitive, dinuclear palladium(I) complexes with 1,1 '-bis(diphenylphosphino)ferrocene (dppf), [Pd-2(dppf)(2)(RNC)(2)](2+) (R = xylyl and mesityl)

    T Tanase; J Matsuo; T Onaka; RA Begum; M Hamaguchi; S Yano; Y Yamamoto

    Reactions of the dinuclear palladium(I) complex, [Pd-2(RNC)(6)](PF6)(2) (R = 2,6-xylyl (Xyl), 2,4,6-mesityl (Mes)), with 1,1'-bis-(diphenylphosphino)ferrocene (dppf) gave dipalladium(I) complexes with dppf ligands, [Pd-2(dppf)(2)(RNC)(2)](PF6)(2) (1, R = Xyl, 66%; 2, R = Mes, 18%), which were characterized by elemental analysis, H-1- and P-31-NMR spectroscopy, IR and UV-vis absorption spectroscopic analyses, and cyclic voltammetry. The structure of 1 was characterized by X-ray crystallography. The cation of compound 1 is composed of two Pd(I) atoms joined by a Pd-Pd sigma-bond (2.602(1) Angstrom) and each palladium ion has a square planar structure ligated by a terminal isocyanide, two P atoms of dppf, and the neighboring Pd atom. The dppf ligands chelate to the metal with an average P-Pd-P bite angle of 99.19 degrees and an average Pd Fe distance of 4.236 Angstrom. The cyclopentadienyl rings of dppf ligands are in staggered form. The H-1- and P-31-NMR and the electronic absorption spectra of 1 and 2 indicated that the metal-metal bonded structure as observed in the crystal of 1 was retained in the solution. Complexes 1 and 2 were extremely photosensitive, and underwent a homolytic cleavage even under a room light. The reaction was monitored by the electronic absorption spectral changes and might generate a cation radical, [Pd(dppf)(ANC)](+). The cyclic voltammograms of 1 and 2 in acetonitrile solution showed two successive quasi-reversible oxidation waves at E-1/2 = 0.60, 0.72 V (vs. Ag/AgPF6) (1) and 0.62, 0.73 V (2) and an irreversible reduction wave at E-1/2 = -1.23 V (1) and -1.22 V (2). The former oxidation waves can be assigned to Fe(II)/Fe(III) processes of the two ferrocenyl groups and demonstrated that a charge-transfer communication between the Fe centers occurred through the Pd-Pd single bond. (C) 1999 Elsevier Science S.A. All rights reserved., 1999年12月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 592 (1), 103 - 108, web_of_science

    研究論文(学術雑誌)

  • 3-Deoxy-D-erythro-hexos-2-ulose bis(thiosemicarbazone) copper(II) chelate. Studies in solution and in the solid state

    S Signorella; C Palopoli; A Frutos; G Escandar; T Tanase; LF Sala

    The 3-deoxy-D-erythro-hexos-2-ulose bis(thiosemicarbazone) (LH2) acts as a tetradentate ligand with S2N2 donor sites to form a copper(II) chelate (Cu(II)L). The Cu K-edge X-ray absorption spectra analysis of a powdered sample revealed a square-planar S2N2 local coordination geometry with average Cu-N and Cu-S distances of 1.92 and 2.33 Angstrom. The EXAFS and XANES spectra and the structural parameters of a DMF solution sample indicate the retention of the square-planar local structure of the Cu(II)S2N2 chromophore upon dissolution. Semiempirical PM3 calculations indicate that the structure of Cu(II)L with the copper(II) ion bound to the S2N2 donor set disposed in a square-planar geometry is the most favorable one (with the highest \Delta H-f\). The formation constant (log K-f = 20.65 +/- 0.06) of the neutral [CuL] species was calculated in 30% v/v dioxane-water and the protonation and deprotonation constants determined., 1999年09月, CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 77 (9), 1492 - 1497, web_of_science

    研究論文(学術雑誌)

  • Peroxo-Bridged Dinuclear Cobalt(III) Complex Containing N-Glycoside Ligands from Tris(2-aminoethyl)amine and D-Glucose or Maltose(α, D-Glucopyranosyl-(1→4)-D-Glucose)

    T Tanase; T Onaka; M Nakagoshi; Kinoshita, I; K Shibata; M Doe; J Fujii; S Yano

    Peroxo-bridged dinuclear cobalt(III) complexes, [{Co((D-Glc)(2)-tren)}(2)(mu-O-2)]X-3. 5H(2)O (X = Cl (2 . 5H(2)O), Br (3 . 5H(2)O)) and [{Co((Mal)(2)-tren)}(2)(mu-O-2)]Cl-3. 6H(2)O (4 . 6H(2)O), were prepared from CoX2. 6H(2)O, tris(2-aminoethyl)amine, and D-glucose (D-Glc) or maltose (alpha-D-glucopyranosyl-(1-->4)-D-glucose; Mal), and were characterized by elemental analysis, UV-vis absorption, circular dichroism, H-1 and C-13 NMR spectroscopic techniques, and X-ray absorption and crystallographic analyses, where (aldose)(2)-tren is bis(N-aldosyl-2-aminoethyl) (2-aminoethyl)amine (aldose D-Glc, Mal). The structure of 2 and 4 were determined by X-ray crystallography to consist of two Co(III) ions bridged by a peroxo unit: 2 . 4H(2)O . CH3OH, orthorhombic, P2(1)2(1)2(1) (No. 19), a = 19.384(8) Angstrom, b = 23.468(5) Angstrom, c = 13.195(5) Angstrom, V = 6002(2) Angstrom(3), Z = 4, D-calcd = 1.440 g cm(-3), T = -99 degrees C, R = 0.078, R-w = 0.085 for 4961 reflections with I > 3 sigma(I); 4 . 2.25H(2)O . 3.75CH(3)OH, monoclinic, P2(1) (No. 4), a = 12.819(7) Angstrom, b = 49.168(18) Angstrom, c = 14.973(6) Angstrom, beta = 104.59(4)degrees, V = 9130(7) Angstrom(3), Z = 4, D-calcd = 1.459 g cm(-3), T = -136 degrees C, R = 0.101 for 6837 reflections with I > 2 sigma(I). The hydrogen bondings between the sugar moieties deviates the Co-O-O-Co torsional angle from planarity to 100.4(6)degrees (2) and av 102(1)degrees (4). The electronic structures of the twisted Co-2(mu-O)(2) core were discussed on the basis of extended Huckel MO calculations. The present discrete complexes have a tetravalent sugar domain around the dinuclear center and clearly demonstrated distinct sugar-sugar interactions which could be a minimal model for so-called sugar clusters of glycoproteins on cell surfaces., 1999年06月, INORGANIC CHEMISTRY, 38 (13), 3150 - 3159, web_of_science

    研究論文(学術雑誌)

  • First synthesis and characterization of zinc(II) complexes containing N-glycosides derived from ethylenediamine and D-glucosamine

    S Yano; S Inoue; Y Yasuda; T Tanase; Y Mikata; T Kakuchi; T Tsubomura; M Yamasaki; Kinoshita, I; M Doe

    Zinc(II) complexes containing N-glycosides derived from D-glucosamine (D-GlcN) and ethylenediamine ten), [Zn(D-GlcN-en)(2)]X-2 (1a X = Cl, 1b X-2 = SO42-), were prepared and characterized by elemental analysis and nuclear magnetic resonance spectroscopy involving X-ray crystallography, where D-GlcN-en = 1 -{(2-aminoethyl)amino}-2-amino-1,2-dideoxy-D-glucose. The complex cation of la has a nearly C-2 symmetry and the central zinc atom is octahedrally coordinated by two tridentate N-glycoside ligands from D-glucosamine and ethylenediamine. The N-glycoside ligand, D-GlcN-en, ligates to the zinc atom through the C-2 amino nitrogen atom of D-glucosamine and the two nitrogen atoms of the diamine in a meridional mode. The analysis of the solution conformation of the sugar ring in la based on vicinal coupling constants confirmed the similar structure revealed by X-ray crystallography., 1999年06月, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (11), 1851 - 1855, web_of_science

    研究論文(学術雑誌)

  • Unprecedented nitrosyl-bridged double-A-frame triplatinum complexes, [Pt-3(mu-triphosphine)(2)(mu-NO)(2)(RNC)(2)](BF4)(4)

    T Tanase; M Hamaguchi; RA Begum; S Yano; Y Yamamoto

    Reaction of linear triplatinum complexes, linear-[Pt-3(mu-dpmp)(2)(RNC)(2)](PF6)(2) 1, with an excess of [NO][BF4] afforded an unprecedented nitrosyl-bridged double-A-frame triplatinum complexes, [Pt-3(mu-dpmp)(2)(mu-NO)(2)(RNC)(2)](BF4)(4) [2a: R = 2,6-xylyl; 2b: R = 2,4,6-mesityl, dpmp = bis(diphenylphosphinomethyl)phenylphosphine], which were characterized by X-ray crystallographic analysis and extended Huckel MO calculations., 1999年04月, CHEMICAL COMMUNICATIONS, (8), 745 - 746, web_of_science

    研究論文(学術雑誌)

  • Ring-fused cyclopropanone N,O-acetals. Electrochemical preparation and their reactivities under acidic conditions

    T Chiba; Saitoh, I; M Okimoto; T Tanase; S Yano

    1999年04月, JOURNAL OF ORGANIC CHEMISTRY, 64 (7), 2516 - 2519, web_of_science

    研究論文(学術雑誌)

  • General Synthesis of Useful Chelating Reagents Having a Sugar Unit, 1,3-Diamino-2-propyl β-D-Glucopyranoside and U, O-Diamino-2-propyl α-D-Mannopyranoside

    S Yano; Y Shinohara; K Mogami; M Yokoyama; T Tanase; T Sakakibara; F Nishida; K Mochida; Kinoshita, I; M Doe; K Ichihara; Y Naruta; P Mehrkhodavandi; P Buglyo; B Song; C Orvig; Y Mikata

    Two 1,3-propanediamine derivatives bearing sugar units, 1,3-diamino-2-propyl beta-D-glucopyranoside (2-beta-D-Glc-pn) and 1,3-diamino-2-propyl alpha-D-mannopyranoside (2-alpha-D-Man-pn), have been prepared and characterized. The structures of two peracetylated diazides, as well as a nickel complex of glucose-type ligand, [Ni(2-beta-D-Glc-pn)(2)SO4] have been determined by X-ray crystallography., 1999年03月, Chemstry Letters, 28 (3), 255 - 256, web_of_science

    研究論文(学術雑誌)

  • Syntheses, characterizations, and redox behavior of optically active viologens and bisviologens

    K Tsukahara; J Kaneko; T Miyaji; K Abe; M Matsuoka; T Hara; T Tanase; S Yano

    Optically active viologens, containing [1-(l-naphthyl)-, 1-phenyl-, and 1-cyclohexylethyl]carbamoylmethyl groups, have been synthesized and characterized. The redox behavior of the chiral viologens was studied compared with achiral viologens. The monoviologens containing naphthyl groups show an intermolecular charge-transfer interaction between the bipyridinium and naphthyl groups in aqueous solution. The association constants are dependent on the chirality of the viologens and larger in the (S,S)- and (R,R)-isomers than in the (R,S)-one. Chiral bisviologens, in which two viologen units are linked with a trimethylene chain, have also been synthesized and characterized. Although the intermolecular charge-transfer interaction between the bipyridinium and viologen units of bisviologens was very weak in solution, such an interaction was appreciably observed in a solid state, which was confirmed by X-ray crystallography. Monoradical trications produced by a one-electron reduction of bisviologens disproportionate more easily in the (R,S)-isomers than in the (S,S)- and (R,R)-ones. The disproportionation is controlled by the steric bulk of the chiral substituents in intramolecular association between two viologen radical units of diradical dications., 1999年01月, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 72 (1), 139 - 149, web_of_science

    研究論文(学術雑誌)

  • Unprecedented Nitrosyl-bridged Double A-Frame Triplatinum Complexes, [Pt3(μ-dpmp)2(μ-NO)2(RNC)2](BF4)4

    TANASE Tomoaki; T. Tanase; M. Hamaguchi; R. A. Begum; S. Yano; Y. Yamamoto

    1999年, Chem. Commun., 745-746

  • Platinum-based Homo- and Heterotrinuclear Transition Metal Complexes Supported by Tridentate Phosphine Ligands

    TANASE Tomoaki; T. Tanase; Y. Yamamoto

    1999年, Trends in Organometallic Chemistry, 3, 35-69

  • A molecular structure of bis(N-octylethylenediamine)zinc(II) nitrate in crystal and the aggregations in wet chloroform and benzene solutions

    M Iida; T Tanase; N Asaoka; A Nakanishi

    Zinc complex with N-octylethylenediamine(= OE), Zn(OE)(2)(NO3)(2), was prepared and its molecular structure was determined on the basis of an X-ray crystallographic analysis. It was revealed that in the octahedral molecular structure the nitrate groups are trans and the octyl chains are transoid. Extensive aggregations of this complex in wet chloroform and wet benzene systems were also studied using H-1 NMR self-diffusions for the solvents and the zinc complex., 1998年12月, CHEMISTRY LETTERS, (12), 1275 - 1276, web_of_science

    研究論文(学術雑誌)

  • Convenient preparation of chiral ethylenediamine linked to D-glucose

    Y Mikata; K Yoneda; T Tanase; Kinoshita, I; M Doe; F Nishida; K Mochida; S Yano

    A useful preparation of an ethylenediamine derivative linked to D-glucose, 2,3-diaminopropyl beta-D-glucopyranoside, has been described. The optically pure compound was obtained conveniently via recrystallization of the diastereomeric mixture of the diazido precursor. The stereochemistry of the ethylenediamino compound was elucidated by X-ray crystallography. (C) 1998 Elsevier Science Ltd. All rights reserved., 1998年12月, CARBOHYDRATE RESEARCH, 313 (3-4), 175 - 179, web_of_science

    研究論文(学術雑誌)

  • Reactions of[η6-C6Me6)RuCl(MDMPP-P, O]and[(η6-C6Me6)RuCl(MDMPP-P, O, O)]Complexes with Lewis Bases or Alkynes, where MDMPP-P, O=P(2-O-6-MeOC6H3)Ph2 and MDMP

    Y Yamamoto; T Tanase; C Sudoh; T Turuta

    Reaction of [(eta(6)-C6Me6)RuCl(MDMPP-P,O)] 1 (MDMPP-P, O=P(2-O-6-MeOC6H3)Ph-2] with CO under high pressure at 95 degrees gave RuCl(CO)(3)(MDMPP-P,O) 2. [(eta(6)-p-cymene)Ru(TDMPP-P,O,O)] (TDMPP-P,O,O=P(2-O-6-MeOC6H3)(2){2,6-(MeO)(2)C6H3}) reacted with CO or CO/2,6-xylyl isocyanide under high pressure to form Ru(CO)(3)(TDMPP-P,O,O) 4 or Ru(CO)(2)(XyINC)(TDMPP-P,O,O) 5 (Xyl = 2,6-Me2C6H3), respectively. Reactions of 1 with Lewis bases in the presence of NH,PF, gave [(eta(6)-C6Me6)RuL(MDMPP-P,O)](PF6) 6 (L = CO, XylNC). Complex 1 reacted with mono-substituted acetylenes in acetone in the presence of bases to form the metal alkynyl complexes [(eta(6)-C6Me6)Ru(C equivalent to CR)(MDMPP-P,O)] 7. Similar reaction of 1 with PhC equivalent to CH in the presence of NaPF6 in acetone or MeOH gave a vinylidene 8a (R=C=CHPh) and a carbene complex 9a (R = CCH2Ph(OMe)) [(eta(6)-C6Me6)Ru(=R)(MDMPP-P,O)](PF6), respectively. A reaction of 1 with HC equivalent to CCMe2OH and NaPF6 in MeOH gave a metallabutadiene complex 10c [(eta(6)-C6Me6) Ru{=C(OMe)CH=CMe2} (MDMPP-P,O)]. X-ray analyses of 6b (L = XylNC), 7a (R = Ph) and 7e (R = CH2OH) were carried out to confirm the structures; 6b, monoclinic, space group P2(1)/c (No. 14), a = 9.910(8) Angstrom, b = 25.370(7) Angstrom, c = 16.020(7) Angstrom, beta = 105.29(5)degrees, V = 3885(7) Angstrom(3), Z = 4, R = 0.050, R-W = 0.053 for 4064 reflections (I > 3.0 sigma(I)); 7a, orthorhombic, space group Pbca, a = 17.222(4) Angstrom, b = 23.772(8) Angstrom, c = 16.003(8) Angstrom, V= 6552(7) Angstrom(3), Z = 8, R = 0.052, R-W = 0.052 for 1836 reflections (I > 3.0 sigma(I)); 7e, triclinic, space group P-1 (No. 2), a = 10.639(4) Angstrom, b = 14.778(3) Angstrom, c = 10.214(3) Angstrom, alpha = 97.05(2)degrees, beta = 113.01(2)degrees, gamma = 79.12(2)degrees, V = 1449(2) Angstrom(3), Z = 2, R = 0.041, R-W = 0.040 for 3270 reflections. (I > 3.0 sigma(I)). (C) 1998 Elsevier Science S.A. All rights reserved., 1998年10月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 569 (1-2), 29 - 37, web_of_science

    研究論文(学術雑誌)

  • Dimolybdenum complexes with a potentially tetradentate PNNP ligand, 2,7-bis(diphenylphosphino)-1,8-naphthyridine (dpnapy)

    T Tanase; T Igoshi; K Kobayashi; Y Yamamoto

    Reaction of cis-[Mo-2(O2CCH3)(2)(CH3CN)(6)] (BF4)(2) with a potentially tetradentate PNNP ligand, 2,7-bis(diphenylphosphino)-1,8-naphthyridine (dpnapy), in a 1:2 molar ratio afforded a mixture of isomeric dimolybdenum complexes, cis-[Mo-2(O2CCH3)(2)(dpnapy-N,P)(2)](BF4)(2) (1) and trans-[Mo-2(O2CCH3)(2)(dpnapy-N,N')(2)] (BF4)(2) (2) in 63 and 5% yields, respectively, which were characterized X-ray crystallography., 1998年09月, JOURNAL OF CHEMICAL RESEARCH-S, (9), 538 - 539, web_of_science

    研究論文(学術雑誌)

  • (μ-Oxo or hydroxo)bis(μ-carboxylato)diruthenium(III) Complexes with Tris(1-pyrazolyl)borate Face-capping Ligand, Affording Versatile Oxidation States via a Protonation/deprotonation Couple

    T Tanase; N Takeshita; S Yano; Kinoshita, I; A Ichimura

    (mu-Oxo or mu-hydroxo)bis(mu-acetate)diruthenium(III) complexes with tris(1-pyrazolyl)borate, [Ru-2(III)(mu-O)(mu-CH3COO)(2)(HBpz(3))(2)] (1) and [Ru-2(III)(mu-OH)(mu-CH3COO)(2)(HBpz(3))(2)](PF6) (2), have been prepared and characterized by X-ray crystallography, and showed a wide range of redox processes, Ru-2(II) <-> (RuRuIII)-Ru-II<->Ru-2(III) <--> (RuRuIV)-Ru-III <-> Ru-2(IV) coupled with protonation/deprotonation at the bridged monoatom., 1998年09月, NEW JOURNAL OF CHEMISTRY, 22 (9), 927 - 929, web_of_science

  • Structure and Magnetic and Electrochemical Properties of(μ-Aryloxo)bis(μ-carboxylato)diruthenium(III) Complexes

    Y Mikata; N Takeshita; T Miyazu; Y Miyata; T Tanase; Kinoshita, I; A Ichimura; W Mori; S Takamizawa; S Yano

    The dinuclear diruthenium complexes ligated by the (mu-aryloxo)bis(mu-carboxylato) system M[Ru2L(mu-O2CR)(2)] (M = Na, R = Me 1; M = Na, R = Ph 2; M = K, R = Me 3; M = K, R = Ph 4; H5L = 2-hydroxy-5-methyl-m-phenylenedimethylenedinitrilotetraacetic acid) were prepared by the reaction of [RuCl2(Me2SO)(4)] with L5- and carboxylic acid. The structure of the benzoate-bridged complex 4 0.5MeOH . 0.5EtOH . 4H(2)O was elucidated by X-ray crystallography. The Ru ... Ru distance was 3.416 Angstrom (average for two crystallographically independent molecules), comparable to those of (mu-alkoxo)bis(mu-carboxylato)diruthenium complexes The magnetic properties were analysed by a general isotropic exchange Hamiltonian H= -2JS(1). S-2 (S-1 = S-2 = 1/2) yielding meaningfully large antiferromagnetic spin coupling constants (-J= 728 and 649 cm(-1) for 1 and 2, respectively). The cyclic voltammogram of 4 in dmf demonstrated two reduction and one oxidation wave corresponding to the four redox states Ru-2(II), (RuRuIII)-Ru-II Ru-2(III), (RuRuIV)-Ru-III. The intervalence coupling constant K-c estimated from the potential gap between Ru-2II/(RuRuIII)-Ru-II and Ru(II)Run(III)/Ru-2(III), indicated that the introduction of the mu-aryloxo bridge stabilizes the (RuRuIII)-Ru-II mixed-valence species., 1998年06月, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (12), 1969 - 1972, web_of_science

    研究論文(学術雑誌)

  • Tetranuclear Iron(III)Complexes with Amino Acids Involving a Planar (μ-Oxo)(μ-hydroxo)bis(μ-alkoxo)bis(μ-carboxylato)tetrairon Core

    T Tanase; T Inagaki; Y Yamada; M Kato; E Ota; M Yamazaki; M Sato; W Mori; K Yamaguchi; M Mikuriya; M Takahashi; M Takeda; Kinoshita, I; S Yano

    Reactions of Fe-III(NO3)(3) . 9H(2)O with 0.5 equivalent of 2-hydroxypropane-1.3-diamine-N,N,N',N'-tetraacetic acid (H(5)dhpta) and an excess of amino acid [glycine (Gly) or L-alanine (L-Ala)] in water with the pH adjusted to ca. 5 by a solution of NaOH gave pale green crystals formulated as Na[Fe-4(dhpta)(2)(mu-O)(mu-OH)(O2CCHRNH3)(2)] (R = H 1 or CH3 2) in moderate yields. The tetrairon(III) complexes were characterized by elemental analyses, IR and Fe-57 Mossbauer spectra, variable-temperature magnetic susceptibility, and X-ray crystallographic and absorption analyses. The structure of 2.6H(2)O was determined by X-ray crystallography to comprise a (mu-oxo)(mu-hydroxo)bis(mu-alkoxo)bis(mu-carboxylato)tetrairon(III) cluster core bridged by two dhpta and two amino acid ligands. Two identical dinuclear iron(III) units [Fe(1)Fe(2) and Fe(3)Fe(4)] are each co-ordinated by a pentadentate dhpta ligand. The Fe(1) and Fe(4) are then bridged by the carboxylate of an amino acid and an oxo group, with the Fe(2) and Fe(3) similarly linked. The central two oxo groups are protonated to form a strongly hydrogen bonded (O-H-O)(3-) bridge [O ... O 2.426(4) Angstrom]. The average Fe Fe distance for the mu-alkoxo dinuclear units is 3.692 A (intradimer) and that for the bis(mu-carboxylato)(mu-oxo/hydroxo)diiron units is 3.463 Angstrom (interdimer), both being in accord with the corresponding values from EXAFS analyses. The two L-alanine moieties are in zwitterionic form and act as interdimer bridging ligands with the carboxylate groups. The Nat counter cation is well packed between the tetrairon(III) complex anions, resulting in an infinite chain aggregation. The Fe-57 Mossbauer spectrum for 2.6H(2)O clearly demonstrated that the four iron sites are equivalent, being in a high-spin octahedral iron(III) state. The variable-temperature magnetic susceptibility measurement for 2.6H(2)O showed modest antiferromagnetism with an interdimer coupling constant (J) of -42.3 cm(-1) and an intradimer coupling constant (J') of -20.8 cm(-1)., 1998年02月, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (4), 713 - 718, web_of_science

    研究論文(学術雑誌)

  • Stereochemistry of nickel(II) complexes with N-glycosylamine ligands from 1,3-diaminopropane and aldopentoses. Correlation between configurational structures and circular dichroism spectra

    T Tanase; Y Yasuda; T Onaka; S Yano

    Reactions of [Ni(tn)(3)]X-2 . 2H(2)O (tn = 1,3-diaminopropane, X = Cl or Br) with aldopentoses afforded a series of mononuclear nickel(II) complexes with N-glycosylamine ligands, [Ni(aldose-tn)(2)]X-2 [aldose-tn = 1-(N-aldosyl)-amino-3-aminopropane, aldose = D-xylose (D-Xyl) 1, D-lyxose (D-Lyx) 2, D-ribose (D-Rib) 3, or D-arabinose (D-Ara) 4], which were characterized by elemental analysis, electronic absorption and circular dichroism (CD) spectroscopy, and X-ray crystallography. Compound 4b, [Ni(D-Ara-tn)(2)]Br-2 . 2H(2)O, was shown by an X-ray analysis to have a C-2 symmetrical mononuclear nickel(II) structure ligated by two tridentate N-glycosylamine ligands, 1-amino-3-(N-D-arabinosyl)propane. The two N-glycosylamines are co-ordinated to the metal through the primary amino and N-glycosidic secondary amino groups and the C-2 hydroxy group of the sugar moiety in a meridional mode, resulting in a Lambda-C-2-helical configuration around the metal centre. The sugar rings adopt an unusual alpha-C-1(4) chair conformation and the sugar-chelate ring conformation is delta. The co-ordination behavior of D-ribose was confirmed by an X-ray analysis of an analogous compound, [Ni(D-Rib-men)(3)]Br-2 . 2CH(3)OH 5 [D-Rib-men = 1-methylamino-2-(N-D-ribosyl)aminoethane], derived from the reaction of [Ni(men)(3)]Br-2 with D-ribose [men : 1-amino-2-(N-methylamino)ethane]. The D-ribose moiety forms an alpha-N-glycosidic bond with the primary amino group of men, and adopts an alpha-C-4(1) chair form, the sugar-chelate ring conformation being delta. The CD spectra of 1-4 were measured in the region 9000-50 000 cm(-1) and clearly indicated the structural features of the complexes; the Cotton effects at around 10 000 cm(-1) (the first absorption band of the d-d transitions) reflected the conformation of the sugar chelate or the absolute configuration of the N-glycosidic nitrogen atom, and those at around 40 000-46 000 cm(-1) (charge-transfer bands) demonstrated the C-2 chiral configuration around the metal centre. These assignments were also confirmed by the CD spectra of known compounds., 1998年02月, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (3), 345 - 352, web_of_science

    研究論文(学術雑誌)

  • Antifungal nickel(II) complexes derived from amino sugars against pathogenic yeast, Candida albicans

    S Yano; S Inoue; R Nouchi; K Mogami; Y Shinohara; Y Yasuda; M Kato; T Tanase; T Kakuchi; Y Mikata; T Suzuki; Y Yamamoto

    Nickel(II) complexes containing N-glycosides derived from D-glucosamine (D-GlcN) and ethylenediamine (en) and trimethylenediamine (tn), [Ni(D-GlcN-en)(2)]Cl-2.H2O (1) (D-GlcN-en = 1-{(2-aminoethyl)amino}-2-amino-1,2-dideoxy-D-glucose) and [Ni(D-GlcN-tn)(2)]Cl-2.4H(2)O (2) (D-GlcN-tn = 1-{(3-aminopropyl)amino}-2-amino-1, 2-dideoxy-D-glucose), are fairly stable in water at room temperature and showed effective antifungal activity against pathogenic yeast, Candida albicans, with the MIC (minimal concentration of inhibition) values of the complexes being 0.25 mM. The results obtained enzyme assays by using preparations of C. albicans chitinase fraction suggested that the sugar complexes 1 and 2 played a role of novel chitinase (chitin-degradation enzyme) inhibitor, where the modes of inhibition were competitive (K-i = 1.3 mM for 1, K-i = 1.8 mM for 2). The newly prepared nickel(II) complex 2 was characterized by elemental analysis, magnetic susceptibility, electronic absorption and circular dichroism spectroscopies, and an X-ray crystallographic analysis. (C) 1998 Elsevier Science Inc. All rights reserved., 1998年02月, JOURNAL OF INORGANIC BIOCHEMISTRY, 69 (1-2), 15 - 23, web_of_science

    研究論文(学術雑誌)

  • Stereochemistry of nickel(II) complexes with N-glycosylamine ligands from 1,3-diaminopropane and aldopentoses. Correlation between configurational structures and circular dichroism spectra

    Tomoaki Tanase; Yukiko Yasuda; Tomoko Onaka; Shigenobu Yano

    Reactions of [Ni(tn)3]X2-2H2O (tn = 1,3-diaminopropane, X = Cl or Br) with aldopentoses afforded a series of mononuclear nickel(u) complexes with N-glycosylamine ligands, [Ni(aldose-tn)2X2 [aldose-tn = l-(W-aldosyl)amino-3-aminopropane, aldose = D-xylose (D-Xyl) 1, o-lyxose (o-Lyx) 2, o-ribose (o-Rib) 3, or o-arabinose (u-Ara) 4], which were characterized by elemental analysis, electronic absorption and circular dichroism (CD) spectroscopy, and X-ray crystallography. Compound 4b, [Ni(D-Ara-tn)2]Br2·2H2O, was shown by an X-ray analysis to have a C2 symmetrical mononuclear nickel(n) structure ligated by two tridentate AT-glycosylamine ligands, l-amino-3-(W-D-arabinosyl)propane. The two N-glycosylamines are co-ordinated to the metal through the primary amino and W-glycosidic secondary amino groups and the C-2 hydroxy group of the sugar moiety in a meridional mode, resulting in a A-C2-helical configuration around the metal centre. The sugar rings adopt an unusual α-1C4 chair conformation and the sugar-chelate ring conformation is 5. The co-ordination behavior of D-ribose was confirmed by an X-ray analysis of an analogous compound, [Ni(D-Rib-men)2Br2-2CH3OH 5 [u-Rib-men = l-methylamino-2-(N-D-ribosyl)aminoethane], derived from the reaction of [Ni(men)3]Br2 with D-ribose [men = l-amino-fW-methylaminoJethane]. The D-ribose moiety forms an α-AT-glycosidic bond with the primary amino group of men, and adopts an a-4C1 chair form, the sugar-chelate ring conformation being 5. The CD spectra of 1-4 were measured in the region 9000-50 000 cm-1 and clearly indicated the structural features of the complexes the Cotton effects at around 10 000 cm-1 (the first absorption band of the d-d transitions) reflected the conformation of the sugar chelate or the absolute configuration of the JV-glycosidic nitrogen atom, and those at around 40 000-46 000 cm-1 (charge-transfer bands) demonstrated the C2 chiral configuration around the metal centre. These assignments were also confirmed by the CD spectra of known compounds., 1998年, Journal of the Chemical Society - Dalton Transactions, (3), 345 - 352, doi

    研究論文(学術雑誌)

  • Site-selective incorporation of zerovalent platinum and palladium fragments into diplatinum centers supported by a triphosphine ligand

    T Tanase; H Ukaji; H Takahata; H Toda; T Igoshi; Y Yamamoto

    Reaction of [Pt-2(RNC)(6)](PF6)(2) (R = 2,6-xylyl (Xyl) (a) and 2,4,6-mesityl (Mes) (b)) with 2 equiv of bis((diphernylphosphino)methyl)phenylphosphine (dpmp) afforded a mixture of isomeric diplatinum complexes, syn-[Pt-2(mu-dpmp)(2)(RNC)(2)](PF6)(2) (1) and anti-[Pt-2(mu-dpmp)(2)(RNC)(2)](PF6)(2) (2), which were purified by cycles of recrystallization and were characterized by X-ray crystallography. Complexes 1 and 2 consist of a diplatinum core (Pt-Pt = 2.7094(8) Angstrom (1a) and 2.683(2) Angstrom (2a)) asymmetrically bridged by two dpmp ligands. The central phosphorus atoms of the dpmp ligands coordinate to the same metal center in the syn-dimer (1) and to different, metal centers in the anti-dimer (2). Complexes 1 and 2 were fluxional in solution through symmetrical structures of syn-1' and anti-2', respectively, in which two terminal phosphine units are uncoordinated. At reflux in CH3CN or by treatment with [Cu(CH3CN)(4)](PF6), complexes ga and 2a lose one isocyanide molecule to be transformed into syn-[Pt-2(mu-dpmp)(2)(XylNC)](PF6)(2) (3, Pt-Pt = 2.6834(8) Angstrom) and anti-[Pt-2(mu-dpmp)(2)(XylNC)](PF6)(2) (4, Pt-Pt; = 2.7150(7) Angstrom), respectively. Reactions of the syn-dimer (1) with [M-3(XylNC)(6)] readily afforded the linearly ordered trinuclear clusters, linear-[Pt2M(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (M = Pt (5), Pd(6)), The additional zerovalent metal atom is incorporated into the terminal position of the trinuclear aggregation, resulting in a d(9)-d(10)-d(9) configuration via one electron transfer from the additional metal to the diplatinum core. The three metal atoms are joined by two metal-metal sigma-bonds (average Pt-Pt = 2.724(2) Angstrom (5), Pt-Pt/Pd = 2.690(1) Angstrom) and are symmetrically bridged by two dpmp ligands, to form a linearly ordered trinuclear structure (Pt-Pt-M = 178.66(8)degrees (5), 180.0 degrees (6)). The similar reactions of the anti-dimer (2) with [M-3(RNC)(6)] led to a formation of the A-frame trinuclear clusters, A-frame-[Pt2M(mu-dpmp)(2)(RNC)(2)](PF6)(2) (7, M = Pt, R = Xyl; 8, M = Pd, R = Mes). The three metal atoms are joined by two metal-metal bonds (Pt-M = 2.6039(7) Angstrom (7), 2.599(3) Angstrom (8)) and asymmetrically bridged by two dpmp ligands, resulting in a so-called trimetallic A-frame structure (Pt-M-Pt = 76.76(3)degrees (7), 78.5(1)degrees (8)). The additional metal is trapped into the middle position of the trinuclear core, through the insertion of d(10) ML2 fragment into the Pt-Pt sigma-bond, which is interestingly contrasted with the terminal position observed in the reactions of the syn-dimer., 1998年01月, ORGANOMETALLICS, 17 (2), 196 - 209, web_of_science

    研究論文(学術雑誌)

  • A Molecular Structure of Bis(octylethylenediamine)zinc((]G0002[))Nitrate in Crystal and the Aggregations in Aqueous Chloroform and Benzene Solutions

    TANASE Tomoaki; M. Iida; T. Tanase; N. Asaoka; A. Nakanishi

    1998年, Chem. Lett., 1275-1276

  • Seven-coordinate manganese(II) complexes with a cage-type N-glycoside ligand. Configurational switch depending on counter anions

    T Tanase; S Tamakoshi; M Doi; W Mori; S Yano

    Configurational switch around the seven-coordinate manganese(II) center ligated by a cage-type N-glycoside ligand was found to depend on its counter anion by X-ray crystallographic analyses of [Mn(aldose(3)-tren)] X-2 (2: aldose = D-mannose, X = Br; 4: aldose = L-rhamnose,X = 1/2SO(4)),where aldose(3)-tren is tris( N-aldosyl-2-aminoethyl)amine. (C) 1997 Elsevier Science S.A., 1997年12月, INORGANICA CHIMICA ACTA, 266 (1), 5 - 7, web_of_science

    研究論文(学術雑誌)

  • Peroxo-bridged dinuclear cobalt(III) complexes containing N-glycoside ligands from tris(2-aminoethyl)amine and D-glucose and their reversible dioxygen binding properties

    T Tanase; T Onaka; M Nakagoshi; Kinoshita, I; K Shibata; M Doe; J Fujii; S Yano

    Peroxo-bridged dinuclear cobalt(III) complexes containing N-glycoside ligands from tris(2-aminoethyl)amine (tren) and D-glucose (D-Glc), [{Co[(D-Glc)(2)tren]}(2)O-2]X-3 . 5H(2)O (X = Cl 2, Br 3), and their reversible dioxygen binding properties are reported [(D-Glc)(2)tren = bis(N-D-glucosyl-2-aminoethyl)(2-aminoethyl)amine]., 1997年11月, CHEMICAL COMMUNICATIONS, (21), 2115 - 2116, web_of_science

    研究論文(学術雑誌)

  • Zero-valent Group 10 metal complexes with a triphosphine ligand, [M(dpmp)(2)], where M=Pt, Pd, Ni, and dpmp=bis(diphenylphosphinomethyl)phenylphosphine

    T Tanase; H Takahata; Y Yamamoto

    Reduction of [MCl2(dpmp)] by NaBH4 in the presence of dpmp afforded zero-valent mononuclear complexes, [M(dpmp)(])2, in good yields (41-86%), where M = Pt (4), Pd (5), Ni (6), and dpmp = bis(diphenylphosphinomethyl)phenylphosphine. The nickel(II) starting complex, [NiCl2(dpmp)] (3), was prepared by the reaction of NiCl2 . 6H(2)O with dpmp and was characterized by X-ray crystallography to be isomorphous with [PdCl2(dpmp)] (2) (3 . CH2Cl2: monoclinic, P2(1)/c, a =10.886(4), b = 21.867(5), c = 13.786(4) Angstrom, V= 3265 Angstrom(3), Z=4, R = 0.071 and R-w = 0.062). The P-31{H-1} NMR spectra of 4-6 were similar to each other showing three multiplets. The structure of 4 was shown by X-ray analysis to have a mononuclear Pt atom tetrahedrally coordinated by two dpmp ligands through four terminal phosphorus atoms (4 . 4C(6)H(6): monoclinic, P2/c, a = 13.563(8), b = 17.098(7), c = 16.995(7) Angstrom, V= 3774 Angstrom(3), Z=2, R = 0.077 and R-w = 0.059). The central P atom of dpmp was uncoordinated. Reaction of 4 with [Pt(XylNC)(4)](PF6)(2) (XylNC = 2,6-xylyl isocyanide) gave a mixture of isomeric diplatinum complexes, syn-and anti-[Pt-2(dpmp)(2)(XylNC)(2)] (PF6)(2) (syn-7 and anti-7). (C) 1997 Elsevier Science S.A., 1997年11月, INORGANICA CHIMICA ACTA, 264 (1-2), 5 - 9, web_of_science

    研究論文(学術雑誌)

  • Di- and trinuclear complexes of palladium with a triphosphine ligand, bis(diphenylphosphinomethyl)phenylphosphine

    T Tanase; H Takahata; M Hasegawa; Y Yamamoto

    Reaction of [Pd(2)(RNC)(6)](PF(6))(2) with dpmp (2 equiv.) generated dipalladium complexes, [Pd(2)(dpmp)(2)(RNC)(2)](PF(6))(2) (1), in good yields, where R = 2,6-xylyl (Xyl) and 2,4,6-mesityl (Mes). Complex 1a (R = Xyl) was characterized by X-ray crystallography to have a metal-metal bonded dinuclear structure (Pd-Pd = 2.607(2) Angstrom) without bridging ligand. The dpmp ligand chelates to the metal through only the terminal phosphorus atoms. Complex la in acetonitrile easily lost one isocyanide ligand and was transformed into a dpmp-bridged dipalladium complex, anti-[Pd(2)(mu-dpmp)(2)(XylNC)](PF(6))(2) . CH(3)CN ((2a)CH(3)CN). The dinuclear core of 2a consists of a three- and a four-coordinate Pd atom bridged by two dpmp ligands (Pd-Pd = 2.702(1) Angstrom). Complex 1a was restored by treatment of 2a with an excess of XylNC. When compound 1 was treated with zero-valent palladium complex [Pd(3)(RNC)(6)], A-frame trinuclear complex, A-frame-[Pd(3)(mu-dpmp)(2)(RNC)(2)](PF(6))(2) (4), was obtained. The trimer 4 was also prepared by the reaction of [Pd(3)(RNC)(8)](PF(6))(2) with dpmp (2 equiv.) via a linear dpmp-bridged trimer, linear-[Pd(3)(mu-dpmp)(2)(RNC)(2)](PF(6))(2) (3). Complex 4a (R = Xyl) was analyzed by X-ray crystallography to be a trinuclear A-frame structure joined by two Pd-Pd sigma-bonds (Pd-Pd = 2.592(2) Angstrom, Pd-Pd-Pd = 79.19(8)degrees). The two dpmp ligands doubly bridge between the three metal atoms. Whereas, complex 4 was thermally and chemically stable, complex 3a (R = Xyl) reacted with I(2) to lead to a trinuclear Pd(II) complex, [{PdI(2)(dpmp)(2)}(2)PdI(2)] (5), which was characterized by an X-ray analysis. The two cis-PdI(2)(dpmp) units were joined by trans-PdI(2) fragment without metal-metal bonds. (C) 1997 Elsevier Science S.A., 1997年10月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 545, 531 - 541, web_of_science

    研究論文(学術雑誌)

  • Chiral inversion around a seven-coordinated cobalt center induced by an interaction between sugars and sulfate anions

    S Yano; M Nakagoshi; A Teratani; M Kato; T Onaka; M Iida; T Tanase; Y Yamamoto; H Uekusa; Y Ohashi

    Novel seven-coordinated cage-type cobalt(II) complexes containing N-glycosides from mannose-type aldoses and tris(2-aminoethyl)amine (tren), [Co((aldose)(3)tren)]X-2.nH(2)O (1a.5H(2)O, aldose=D-mannose (D-Man), X = Cl-; 1b.5H(2)O, aldose = 6-deoxy-L-mannose (L-Rha), X = Cl-; 2a.4H(2)O, aldose = D-Man, X = Br-; 2b.H2O, aldose = L-Rha, X = Br-) and [Co((aldose)(3)tren)]SO4.nH(2)O (3a.4H(2)O, aldose = D-Man; 3b.3H(2)O, aldose = L-Rha), where (aldose)(3)tren is tris(2-(aldosylamino)ethyl)amine, were prepared and characterized by elemental analysis, electronic absorption and circular dichroism spectroscopies, and X-ray crystallography. Crystal data are as follows. 2b.2CH(3)OH: C26H56N4O14Br2Co, monoclinic, space group P2(1), a=11.045(2) Angstrom, b=17.283(6) Angstrom, c=10.996(3) Angstrom, beta=117.371(6)degrees, V=1864(1) Angstrom(3), Z=2, R=0.072 for 2787 independent reflections. 3b.3H(2)O.CH3OH:C25H58N4O20SCo, orthorhombic, space group P2(1)2(1)2(1), a=14.836(2) Angstrom, b=22.489(2) Angstrom, c=12.181(3) Angstrom, V=4064(1) Angstrom(3), Z=4, R=0.077 for 2010 independent reflections. The complex cation of 2b consists of a cobalt atom coordinated by a heptadentate (L-Rha)(3)tren ligand to produce a mono-face-capped octahedron having pseudo-C-3 symmetry with-a Lambda (lambda(3)-ob form) configuration around the metal. The complex cation of 3b has a monoface-capped octahedron coordinated by a heptadentate (L-Rha)(3)tren ligand having pseudo-C-3 symmetry with a Delta (lambda(3)-lel form) configuration. The other facial site of the complex cation is capped by the SO42- anion through hydrogen banding with the hydroxy groups of L-rhamnose residues. The C-3 helical-configurational inversion around the cobalt(II) center, Delta < -- > Lambda, induced by an interaction between the sugars and the SO42- anion, was monitored by circular dichroism spectroscopy, for which the sign of the Cotton effect of 1 and 2, having halide counteranions, is opposite to that of 3, having sulfate counteranions, and was found to proceed reversibly upon addition and removal of sulfate anions. The intensities of circular dichroism spectra for [Co((L-Rha)(3)tren)](2+) and [Co((D-Man)(3)tren)](2+) were appreciably changed upon addition of sulfate ions. The spectral changes were interpreted in terms of ion-pair formation. On the basis of electrostatic theories of ion association, the closest distance between the sulfate ion and the [Co((D-Man or L-Rha)(3)tren)](2+) cation was estimated as similar to 5 Angstrom, which is consistent with the Co-S distance of 4.697(6) Angstrom observed in the crystal structure of 3b. The sulfate ion was suggested to fit into the cavity composed of the sugar hydroxyl groups through hydrogen bonds even in the solution state., 1997年09月, INORGANIC CHEMISTRY, 36 (19), 4187 - 4194, web_of_science

    研究論文(学術雑誌)

  • Trimanganese complexes with a linear MnIIMnIIIMnII assemblage bridged by carbohydrates

    S Yano; M Doi; S Tamakoshi; W Mori; M Mikuriya; A Ichimura; Kinoshita, I; Y Yamamoto; T Tanase

    Reaction of manganese(II) salts (MnX2 . nH(2)O, X = Cl, Br, NO3) with tris[(N-aldosyl)aminoethyl] amines L-n, prepared by the reaction between tris(aminoethyl)amine (tren) with aldose [D-mannose (D-man) (L-1)] or L-rhamnose [L-rha = 6-deoxy-L-man) (L-2)] in situ, affords red-orange crystals formulated as [(MnLn)(2)Mn(H2O)]X-3 (n = 2, X = Cl 1; n = 2, X = Br 2; n = 2, X = NO3 3; n = 1, X = Cl 4), complexes 3 and 4 are characterized by X-ray crystallography., 1997年06月, CHEMICAL COMMUNICATIONS, (11), 997 - 998, web_of_science

    研究論文(学術雑誌)

  • A-Frame Trinuclear Complexes of Platinum and Palladium with a Tridentate Phosphine Ligand. Insertion of d10 Pt(0) and Pd(0)Fragments into a Pt-Pt σ-Bond

    T Tanase; H Takahata; H Ukaji; M Hasegawa; Y Yamamoto

    Reactions of anti-[Pt-2(mu-dpmp)(2)(RhrC)(2)](PF6)(2) (3) (dpmp = bis(diphenylphosphinomethyl)phenylphosphine) with [M-3(RNC)(6)] (M = Pt, Pd) afforded trimetallic A-frame clusters, [Pt2M(mu-dpmp)(2)(RNC)(2)](PF6)(2) (6: M = Pt, R = xylyl (Xyl); 7: M = Pd, R = mesityl (Mes)). The d(10) Pt-0(RNC)(2) and Pd-0(RNC)(2) fragments were shown to be inserted into the Pt-Pt sigma-bond of complex 3 by spectroscopic and X-ray crystallographic analyses. The uncoordinated phosphine units in 3 enable the d(10) metal to sit in the middle position of the trinuclear array. The similar A-frame tripalladium complexes, [Pd-3(mu-dpmp)(2)(RNC)(2)](PF6)(2) (8a: R = Xyl; 8b: R = Mes), were also prepared by the reaction of [Pd-3(RNC)(8)](PF6)(2) with dpmp., 1997年06月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 538 (1-2), 247 - 250, web_of_science

    研究論文(学術雑誌)

  • Incorporation of group 11 metal ions into a diplatinum center leading to Pt(2)M heterotrinuclear complexes supported by a tridentate phosphine ligand (M=Au, Ag, Cu)

    T Tanase; H Toda; Y Yamamoto

    The reaction of syn-[Pt-2(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (1) with AuPF6 yielded the Pt2Au trinuclear complex [Pt2Au(mu-dpmp)(2)(XylNC)(2)](PF6)(3) (7) in 60% yield. The structure was determined by X-ray crystallography to comprise a Pt2Au trinuclear core bridged by two dpmp ligands (7 .(CH3)(2)CO: monoclinic, P2(1)/n (No. 14), a = 15.147(3) Angstrom, b = 25.947(8) Angstrom, c = 25.759(6) Angstrom, beta = 104.10(2)degrees, V = 9818 Angstrom(3), Z = 4, D-calcd = 1.593 g cm(-3), R = 0.065, and R(w) = 0.059). An Au(I) ion is trapped by two uncoordinated phosphine units in 1 to lead a deformed Pt-Pt-Au aggregation. The Pt-Pt and Pt ... Au distances are 2.708(2) and 3.045(2) Angstrom, respectively, and the Pt-Pt ... Au angle is 110.68(5)degrees. The similar Pt2Ag cluster, [Pt2Ag(mu-dpmp)(2)(XylNC)(2)](PF6)(3) (8), was also prepared by the reaction of complex 1 with AgPF6 in 70% yield. The crystal structure is essentially identical to that of 7 (monoclinic, C2/c(No. 15), a = 18.302(6) Angstrom, b = 25.056(6) Angstrom, c = 47.172(9) Angstrom, beta = 99.11(3)degrees, V = 21359 Angstrom(3), Z = 8, D-calcd = 1.373 g cm(-3), R = 0.089, and R(w) = 0.078). The Pt-Pt and Pt ... Ag distances are 2.657(2) and 3.118(3) Angstrom, respectively, and the Pt-Pt ... Ag angle is 136.36(8)degrees. Reactions of 1 with CuX (X = I, Pr, Cl) gave yellow complex [Pt(2)CuX(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (9, X = I; 10, X = Pr; 11, X = Cl), in good yield (9 . Et(2)O: monoclinic, P2(1)/c (No. 14), a = 15.048(4) Angstrom, b = 21.922(3) Angstrom, c = 27.840(3) Angstrom, beta = 101.89(1)degrees, V = 8987 Angstrom(3), Z = 4, D-calcd = 1.641 g cm(-3), T = 23 degrees C, R = 0.056, and R(w) = 0.046. 10 . Et(2)O: monoclinic, P2(1)/c (No. 14), a = 14.910(4) Angstrom, b = 21.891(7) Angstrom, c = 27.226(8) Angstrom, beta = 101.66(6)degrees, V = 8702 Angstrom(3), Z = 4, D-calcd = 1.658 g cm(-3), T = -95 degrees C, R = 0.042, and R(w) = 0.046. 11 . Et(2)O: monoclinic, P2(1)/c (No. 14), a = 15.037(4) Angstrom, b = 22.081(6) Angstrom, c = 27.449(4) Angstrom, beta = 101.92(2)degrees, V = 8917 Angstrom(3), Z = 4, D-calcd = 1.585 g cm(-3), T = 23 OC, R = 0.040, and R(w) = 0.041). The Pt(2)CuX assembly forms a rhombic structure with the Pt-Pt, Pt ... Cu, Cu-X, and Pt ... X distances being 2.715-2.727, 2.857-2.872, 2.276-2.597, and 3.088-3.130 Angstrom, respectively. The CuI fragment is trapped by the pendant phosphorus arms of 1. The Pt ... Cu-X angle is interestingly less than 90 degrees, resulting in a relatively short interatomic distance between the terminal Pt and X atoms. A monovalent group 11 metal ion (Au(I), Ag(I), or Cu(I)), which has a d(10) configuration, was readily incorporated into the Pt-2 core, leading to a heterotrimetallic Pt(2)M aggregation., 1997年04月, INORGANIC CHEMISTRY, 36 (8), 1571 - 1577, web_of_science

    研究論文(学術雑誌)

  • Synthesis and characterization of quadruply bonded dinuclear molybdenum(II) complexes with bis(diphenylphosphinomethyl)phenylphosphine and oxidation of the triphosphine ligand

    T Tanase; T Igoshi; Y Yamamoto

    Reaction of cis-[Mo-2(O2CR)(2)(MeCN)(6)] (BF4)(2) (1) with 2 equiv, of tridentate phosphine, bis(diphenylphospdinomethyl)-phenylphosphine (dpmp), afforded trans-[Mo-2(O2CR)(2)(dpmp)(2)] (BF4)(2) (2a: R = Me; 2b: R = Bu-t; 2c: R = Ph), which were characterized by X-ray crystallography (2a: monoclinic, P2(1)In, a = 11.329(2), b = 18.439(4), c = 18.101(2) Angstrom, beta = 97.81(1)degrees, Z = 2, R = 0.063 and R-W = 0.068 for 2186 reflections with I > 3 sigma(I); 2b: monoclinic, P2(1)In, a = 13.29(1), b = 19.979(3), c = 14.265(3) Angstrom, beta = 100.37(3)degrees, Z = 2, R = 0.043 and R-W = 0.049 for 3746 reflections with I>3 sigma(I); 2b: monoclinic, P2(1)In, a = 14.52(1), b = 17.253(4), c = 18.985(3) Angstrom, beta = 104.34(4)degrees, Z = 2, R = 0.065 and R-W = 0.069 for 2019 reflections with I > 3 sigma(I)). Complexes 2 comprise a quadruply bonded dimolybdenum(II) structure (Mo-Mo = 2.119(3) Angstrom (2a), 2.115(1) Angstrom (2b), and 2.131(4) Angstrom (2c)) bridged by two carboxylate and two dpmp ligands with a trans geometry. The two dpmp ligands take a head-to-tail arrangement and act as bidentate ligands with a terminal and the central phosphorus atoms; the remaining terminal P atom is uncoordinated. Treatment of complexes 2a-c with dioxygen gave ligand-oxidized dimolybdenum(II) complexes, trans- [Mo-2(O2CR)(2)(dpmp-O)(2)] (BF4)(2) (3a: R = Me; 3b: R = Bu-t; 3c: R = Ph), where dpmp-O = Ph2PCH2PPhCH2P(=O)Ph-2. X-ray crystallographic analyses of 3a and 3c demonstrated that the uncoordinated phosphorus atom of dpmp in 2a,c was converted into phosphine oxide in 3a,c and the P = O unit is coordinated to the Mo atom in the axial position via the oxygen atom (3a: monoclinic, P2(1)In, a = 11.414(4), b = 18.33(1), c = 18.112(7) Angstrom, beta = 97.57(3)degrees, Z = 2, R = 0.052 and R-W = 0.058 for 2218 reflections with I > 3 sigma(I); 3c: monoclinic, P2(1)In, a = 14.554(8), b = 17.182(3), c = 18.768(2) Angstrom, beta = 104.25(2)degrees, Z = 2, R = 0.058 and R-W = 0.062 for 3888 reflections with I > 3 sigma(I))., 1997年03月, INORGANICA CHIMICA ACTA, 256 (1), 61 - 67, web_of_science

    研究論文(学術雑誌)

  • Platinum-based heterotrinuclear complexes involving a group 9 metal ion: MCl(isocyanide)-fragment-capped Pt(2)M T-shaped clusters (M=Rh(I), Ir(I))

    T Tanase; H Toda; K Kobayashi; Y Yamamoto

    Reactions of syn-[Pt-2(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (1), where dpmp = bis((diphenylphosphino)methyl)-phenylphosphine and Xyl = 2,6-xylyl, with [MCl(cod](2) (M = Rh, Ir) afforded the linearly ordered Pt-Pt-M clusters [Pt-2{MCl(XylNC)}(mu-dpmp)(2)(XylNC)](PF6)(2) (6a, M = Rh; 6b, M = Ir) and the asymmetrical A-frame clusters [Pt-2{M(XylNC)}mu-Cl)(mu-dpmp)(2)(XylNC)](PF6)(2) (7a, M = Rh; 7b, M = Ir). The structures of 6a and 6b as well as that of 7a were determined by X-ray crystallography to reveal that the trinuclear core of the linearly ordered clusters 6 is joined by two metal-metal bonds in which the Pt-Pt and Pt-M bonds can be viewed respectively, as d(9)-d(9) covalent and a d(9)<--d(8) dative interactions., 1996年12月, ORGANOMETALLICS, 15 (25), 5272 - 5274, web_of_science

    研究論文(学術雑誌)

  • Carboxylate- and phosphate ester-bridged dimagnesium(II), dizinc(II), and dicalcium(II) complexes. Models for intermediates in biological phosphate ester hydrolysis

    JW Yun; T Tanase; SJ Lippard

    Carboxylate-bridged dimagnesium(II) complexes were synthesized and characterized by employing the dinucleating ligand XDK, where H(2)XDK is m-xylylenediamine bis(Kemp's triacid imide). The reaction of 1 or 2 equiv of sodium diphenyl phosphate with [Mg-2(XDK)(CH3OH)(4)(H2O)(2)(NO3)](NO3), 1(NO3), afforded [Mg-2(XDK){mu-eta(2)-(PhO)(2)PO2}(CH3OH)(3)(H2O)(NO3)]. 3CH(3)OH(2 . 3CH(3)OH) and [Mg-2(XDK){mu-eta(2)-(PhO)(2)PO2},{eta(1)-(PhO)(2)PO2}(CH3OH)(3)(H2O)]. CH3OH(3 . CH3OH), respectively. These are the first structurally characterized phosphate ester-bridged dimagnesium(II) complexes. The reaction of 1 with 1 equiv of bis(4-nitrophenyl) hydrogen phosphate resulted in protonation of one of the carboxylate ligands and liberation of one magnesium(II) ion to give [Mg(HXDK)(2)(H2O)(2)](4), an octahedral complex containing two short, low barrier intramolecular OH ... O hydrogen bonds. The phosphate ester exchange rate of free and bound diphenyl phosphate in 3 in methanol solution was measured by variable-temperature P-31{H-1} NMR spectroscopy and compared to that of structurally analogous dizinc(II), [Zn-2(XDK){mu-eta(2)-(PhO)(2)PO2},{eta(1)-(PhO)(2)PO2}(CH3OH)(2)(H2O)] (5), and dicalcium(II), [Ca-2(XDK){mu-eta(2)-(PhO)(2)PO2},{eta(1)-(PhO)(2)PO2}(CH3OH)(3)(H2O)]. CH3OH), complexes. The synthesis and structural characterization of 6 is presented, along with a discussion of the differences between the carboxylate- and phosphate ester-bridged dimagnesium(II), dizinc(II), and dicalcium(II) centers. Crystallographic data are as follows. 1(NO3): monoclinic, P2(1)/c, a = 11.240(3) Angstrom, b = 13.019(2) Angstrom, c = 30.208(7) Angstrom, beta = 99.11(1)degrees, V = 4365(2) Angstrom(3), Z = 4, R = 0.045, and R(w) = 0.054 for 5021 independent reflections with I > 3 sigma(I). 2 . 3CH(3)OH: monoclinic, P2(1)/c, a = 16.611(5) Angstrom, b = 16.059(6) Angstrom, c = 21.930(9) Angstrom, beta = 93.34(6)degrees, V = 5840(4) Angstrom(3), Z = 4, R = 0.069, and R(w) = 0.085 for 3759 independent reflections with I > 2 sigma(I). 3 . CH3OH: monoclinic, P(2)1/n, a = 18.912(4) Angstrom, b = 16.254(2) Angstrom, c = 21.646(5) Angstrom, beta = 112.26(2)degrees, V = 6158(2) Angstrom(3), Z = 4, R = 0.060, and R(w) = 0.072 for 5184 independent reflections with I > 3 sigma(I). 4: monoclinic, P2(1)/n, a = 15.210(5) Angstrom, b = 15.772(3) Angstrom, c = 13.093(3) Angstrom, beta = 96.35(3)degrees, V = 3122(1) Angstrom(3), Z = 2, R = 0.069, and R(w) = 0.070 for 1840 independent reflections with I > 2 sigma(I). 6 . CH3OH: monoclinic, P2(1)/n, a = 16.5471(3) Angstrom, b = 24.3415(6) Angstrom, c = 16.5865(3) Angstrom, beta = 104.2530(10)degrees, V = 6475.1(2) Angstrom(3), Z = 4, R = 0.053, and wR(2) = 0.142 for 7858 independent reflections with I > 2 sigma(I)., 1996年12月, INORGANIC CHEMISTRY, 35 (26), 7590 - 7600, web_of_science

    研究論文(学術雑誌)

  • A diruthenium(II) complex containing an unprecedented bridging S,O-bidentate dimethyl sulfoxide ligand

    T Tanase; T Aiko; Y Yamamoto

    The diruthenium(II) complex [Ru-2(mu-Cl)(mu-H)(mu-Me(2)SO)- Cl-2(Me(2)SO)(4)]. 2CH(2)Cl(2) is prepared from [RuCl2(Me(2)SO)(4)] in methanol in the presence of Na-2(xdk) [H(2)xdk = m-xylenediamine bis(Kemp's triacid imide)] and characterized by X-ray crystallography which reveals an unprecedented S,O-bidentate bridging Me(2)SO ligand., 1996年10月, CHEMICAL COMMUNICATIONS, (20), 2341 - 2342, web_of_science

    研究論文(学術雑誌)

  • Formation of heterocyclic compounds from reactions of dicobalt octa(xylyl isocyanide) with chloroacetone or methyl monochloroacetate

    K Sugano; T Tanase; Y Yamamoto

    Reaction of xylyl isocyanide with chloroaretone in the presence of [Co2(XylNC)(8)] (Xyl = 2,6-Me(2)C(6)H(3)) gave the derivatives of azacyclopent-3-ene (CH3COCH3)(XylNC)(4) 1 and cobaltaazacyclobutane CoCl(CH3COCH)(XylNC)(5) 2. Similar reaction with methyl monochloroacetate gave the analog of 1 (CH(3)COOMe)(XylNC)(4) 4 and the 2,6-diaza-bicyclo[3,3,0]octa-1,7-diene derivative (CHCOOMe)(XylNC)(5) . C6H6 5 C6H6. Compounds 1 and 5 C6H6 Were confirmed by their X-ray analyses (1 monoclinic, space group Cc (No. 9), a = 10.241(3), b = 19.474(6), c = 16.955(8) Angstrom, beta = 103.42(3)degrees, V = 3289(2) Angstrom(3), Z = 4, and R = 0.043; 5 . C6H6 or thorhombic, space group Pbcn (No. 60), a = 21.642(5), b = 14.028(3), c = 30.449(8) Angstrom, V = 9244(7) Angstrom(3), Z = 8, and R = 0.087). A possible reaction route is discussed., 1996年10月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 523 (2), 197 - 204, web_of_science

    研究論文(学術雑誌)

  • Synthesis, Structures, and Spectroscopic, Magnetic, and Electrochemical Properties of (μ-Alkoxo)bis(μ-carboxylato)diruthenium Complexes, M[Ru2(dhpta)(μ-O2CR)2](M=Na and K, dhptaH5=1,3-diamino-2-hydroxy-propane t

    T Tanase; Y Yamada; K Tanaka; T Miyazu; M Kato; K Lee; Y Sugihara; W Mori; A Ichimura; Kinoshita, I; Y Yamamoto; M Haga; Y Sasaki; S Yano

    [RuCl2(dmso)(4)] (dmso = dimethyl sulfoxide) was treated with dhptaH(5) (1,3-diamino-2-hydroxypropanetetraacetic acid) and carboxylate ligands in the presence of NaOH or KOH and gave dinuclear ruthenium(III) complexes of dhpta with two bridging carboxylates, M[Ru(dhpta)(mu-O(2)CR)(2)] (1, R = C6H5, M = Na; 1', R = C6H5, M = K; 2, R = p-OHC6H4, M = Na; 3, R = p-NH2C6H4, M = Na; 4, R = CH3, M = Na; 4', R = CH3, M = K), which were characterized by elemental analysis, mass, electronic absorption, and H-1 and C-13 NMR spectroscopies, and X-ray absorption and crystallographic analyses (4, orthorhombic, space group Pca2(1) with a = 21.359(4) Angstrom, b = 7.484(2) Angstrom, c = 12.930(2) Angstrom, Z = 4, R = 0.065, and R(w) = 0.044 for 1116 independent reflections with I > 3 sigma(I); 4'. 1.5H(2)O: monoclinic, P2(1), a = 7.689(2) Angstrom, b = 17.213(2) Angstrom, c = 18.103(2) Angstrom, beta = 94.50(1)degrees, Z = 4; R = 0.041, and R(w) = 0.047 for 4705 independent reflections with I > 3 sigma(I)). The complex anion consists of two ruthenium atoms bridged by the alkoxide of dhpta and the two acetate ligands. The Ru-Ru distances of 3.433(3) Angstrom (4) and 3.421(1) Angstrom (average) (4') are longer than those found in (mu-oxo)bis(mu-carboxylato)diruthenium(III) complexes. EXAFS analysis and H-1 NMR spectra indicated that complexes 1-4 have the identical dinuclear structure in both solid and water solution states. Temperature-dependent magnetic susceptibility of 1-4 showed a strong antiferromagnetic interaction between the two Ru(III) ions with -J = 310-470 cm(-1). Cyclic voltammograms showed two reduction processes at ca. -0.34 and ca. -0.94 V vs Ag/AgCl, corresponding to two stepwise one-electron reductions, (RuRuIII)-Ru-III <-> (RuRuII)-Ru-III <-> (RuRuII)-Ru-II. The most remarkable feature is the large separation between the two redox potentials, implying that the mixed-valence diruthenium(III,II) complexes of dhpta are fairly stable. Potentiostatic electrolysis of 1-4 at a potential in between E(1/2)(1) and E(1/2)(2) consumed 1 F per dimer and afforded a mixed-valence diruthenium species, [(RuRuIII)-Ru-II(dhpta)mu-O(2)CR)(2)](2-), in solution, which showed two weak and broad absorption bands (nu(max) 5.5-5.7 and 11.6-11.9 kcm(-1)) in DMF assignable to intervalence charge transfer (IT) bands. The lower energy IT band was analyzed by Gaussian curve fitting and the electron exchange integral H-ad was estimated as 640-870 cm(-1) on the basis of Hush's theory. The spectroscopic analysis indicated that [(RuRuIII)-Ru-II(dhpta)(O(2)CR)(2)](2-) belongs to Class II type mixed-valence diruthenium complexes., 1996年10月, INORGANIC CHEMISTRY, 35 (21), 6230 - 6239, web_of_science

    研究論文(学術雑誌)

  • Successful isolation and X-ray crystal structure of (tris(N-L-rhamnosyl-2-aminoethyl)amine)(sulfate) nickel(II) hydrate trimethanol solvate: [Ni((L-Rha)(3)-tren)(SO4)]center dot H2O center dot 3CH(3)OH

    S Yano; M Doi; M Kato; Okura, I; T Nagano; Y Yamamoto; T Tanase

    We have succeeded in the isolation and X-ray crystal structure determination of the octahedral nickel(II) complex [Ni((L-Rha)(3)-tren) (SO4)]. H2O . 3CH(3)OH (tren = tris(2-aminoethyl)amine; Rha = rhamnose) containing an N-glycoside derived from the reaction of L-Rha and tren. Crystal data: C27H62N4O20SNi, M(r) = 853.56, orthorhombic, space group P2(1)2(1)2(1), a = 16.035(4), b = 16.670(7), c = 15.38(1) Angstrom, Z = 4., 1996年08月, INORGANICA CHIMICA ACTA, 249 (1), 1 - 3, web_of_science

    研究論文(学術雑誌)

  • Assembly of carbohydrates on a nickel(II) center by utilizing N-glycosidic bond formation with tris(2-aminoethyl)amine (tren). Syntheses and characterization of [Ni{N-(aldosyl)-tren}(H2O)](2+), [Ni{N,N'-bis(aldosyl)-tren}](2+) and [Ni{N,N',N''-tris(aldosyl)-tren}](2+)

    T Tanase; M Doi; R Nouchi; M Kato; Y Sato; K Ishida; K Kobayashi; T Sakurai; Y Yamamoto; S Yano

    Reactions of [Ni(tren)(H2O)(2)]X(2) (tren = tris(2-aminoethyl)amine; X = Cl (1a), Br (1b); X(2) = SO4 (1c)) with mannose-type aldoses, having a 2,3-cis configuration (D-mannose and L-rhamnose), afforded {bis(N-aldosyl-2- aminoethyl) (2-aminoethyl)amine}nickel(II) complexes, [Ni(N,N'-(aldosyl)(2)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (2a), Br (2b), X(2) = SO4 (2c); aldosyl = L-rhamnosyl, X(2) = SO4 (3c)). The structure of 1c was confirmed by X-ray crystallography to be a mononuclear [(NiN4O2)-N-III] complex with the tren acting as a tetradentate ligand (1c . 2H(2)O: orthorhombic, Pbca, a = 15.988(2) Angstrom, b = 18.826(4) Angstrom, c = 10.359(4) Angstrom, V = 3118 Angstrom(3), Z = 8, R = 0.047, and R(w) = 0.042). Complexes 2a,c and 3c were characterized by X-ray analyses to have a mononuclear octahedral Ni(II) structure ligated by a hexadentate N-glycoside ligand, bis(N-aldosyl-2-aminoethyl) (2-aminoethyl)amine (2a . CH3OH: orthorhombic, P2(1)2(1)2(1), a = 16.005(3) Angstrom, b = 20.095(4) Angstrom, c = 8.361(1) Angstrom, V = 2689 Angstrom(3), Z = 4, R = 0.040, and R(w) = 0.027. 2c . 3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.93(2) Angstrom, b = 21.823(8) Angstrom, c = 9.746(2) Angstrom, V = 3176 Angstrom(3), Z = 4, R = 0.075, and R(w) = 0.080. 3c . 3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.560(4) Angstrom, b = 21.694(5) Angstrom, c = 9.786(2) Angstrom, V = 3091 Angstrom(3), Z = 4, R = 0.072, and R(w) = 0.079). The sugar part of the complex involves novel intramolecular sugar-sugar hydrogen bondings around the metal center. The similar reaction with D-glucose, D-glucosamine, and D-galactosamine, having a 2,3-trans configuration, resulted in the formation of a mono(sugar) complex, [Ni(N-(aldosyl)-tren)(H2O)(2)]Cl-2 (aldosyl = D-glucosyl (4b), 2-amino-2-deoxy-D-glucosyl (5a), and 2-amino-2-deoxy-D-galactosyl (5b)), instead of a bis(sugar) complex. The hydrogen bondings between the sugar moieties as observed in 2 and 3 should be responsible for the assembly of two sugar molecules on the metal center. Reactions of tris(N-aldosyl-2-aminoethyl)amine with nickel(II) salts gave the tris(sugar) complexes, [Ni(N,N',N''-(aldosyl)(3)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (6a), Br (6b); L-rhamnosyl, X = Cl (7a), Br (7b); D-glucosyl, X = Cl (9); maltosyl, X = Br (10); and melibiosyl, X = Br (11)), which were assumed to have a shuttle-type C-3 symmetrical structure with Delta helical configuration for D-type aldoses on the basis of circular dichroism and C-13 NMR spectra. When tris(N-rhamnosyl)-tren was reacted with NiSO4 . 6H(2)O at low temperature, a labile neutral complex, [Ni(N,N',N''-(L-rhamnosyl)(3)-tren)(SO4)] (8), was successfully isolated and characterized by X-ray crystallography, in which three sugar moieties are anchored only at the N atom of the C-1 position (8 . 3CH(3)OH . H2O: orthorhombic, P2(1)2(1)2(1), a = 16.035(4) Angstrom, b = 16.670(7) Angstrom, c = 15.38(1) Angstrom, V = 4111 Angstrom(3), Z = 4, R = 0.084, and R(w) = 0.068). Complex 8 could be regarded as an intermediate species toward the C-3 symmetrical tris(sugar) complexes 7, and in fact, it was readily transformed to 7b by an action of BaBr2., 1996年08月, INORGANIC CHEMISTRY, 35 (17), 4848 - 4857, web_of_science

    研究論文(学術雑誌)

  • Dinuclear palladium(I) complexes with isocyanide and N-donor bidentate ligands

    T Tanase; H Ukaji; Y Yamamoto

    Reactions of the dinuclear palladium(I) complex [Pd2Cl2(RNC)(4)] (R=2,4,6-Me(3)C(6)H(2)) 1 with the N-donor compounds 2,2'-bipyridyl (bipy), 1,10-phenanthroline (phen), and 2,9-dimethyl-1, 10-phenanthroline (dmphen) gave dipalladium(I) complexes with chelating N-donor ligands, [Pd-2(RNC)(2)L(2)] [PF6](2) (L=bipy 2, phen 3 or dmphen 4). The structures of 2 and 4 were characterized by X-ray crystallography. The cation of 2 is composed of two Pd atoms joined by a sigma bond [2.518(3)Angstrom] each of which has a square-planar co-ordination involving a terminal isocyanide and a chelating bipy ligand. Complex 3 is expected to have a structure similar to 2 on the basis of spectroscopic data. Complex 4 exhibits a distorted dinuclear structure due to the steric bulk of the N-donor ligand. The Pd-Pd bond length is 2.599(2)Angstrom. Each dmphen ligand; chelates to a Pd atom and the isocyanide acts as a semibridging ligand. The similar reactions of complex 1 with 2,2'-biquinoline (bquin) and 1,8-naphthyridine (napy) afforded the isocyanide-bridged dipalladium(I) complexes, [Pd-2(mu-RNC)(2)(bquin)(2)]-[PF6](2) 5 and [Pd-2(mu-RNC)(2)(napy)(4)] [PF6](2) 6, in 24-36% yields. Complex 6 comprises a dinuclear palladium(I) core bridged by two isocyanide ligands [Pd-Pd 2.747(4)Angstrom] with four terminal napy ligands co-ordinated in a monodentate fashion., 1996年07月, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (14), 3059 - 3064, web_of_science

    研究論文(学術雑誌)

  • Spontaneous multiple insertion of a bulky aromatic isocyanide into the palladium-hydride bond of trans-[Pd(H)Cl(PPh(3))(2)], leading to formation of heterobicyclic and pyrrole compounds

    T Tanase; T Ohizumi; K Kobayashi; Y Yamamoto

    The reaction of [PdCl2(PPh(3))(2)] (1) with an excess of 2,6-xylyl isocyanide (XylNC) and H(2)SiMePh in refluxing toluene gave a mononuclear palladium complex of a polyimino ligand, [Pd{C(=NR)C(=NR)C(=NR)C(=NR)CH(=NR)}(C=NR)Cl]. 1/2C(6)H(6)(3 . 1/2C(6)H(6): R = Xyl, 30%), and a novel heterobicyclic compound, 2,6-(2',6'-xylyl)(2)-3,7-(N-2',6'-xylylimino)(2)-4,8-(N-2',6'-xylylamino)(2)-2,6-diazabicyclo[3.3.0]octa-4,8-diene (4a, 15%), structures of which were determined by X-ray analyses. When the reaction was carried out in the presence of triethylamine, the yield of 4a increased up to 44%. The complex 3 involves a pentaimino moiety [-C(=NR){C(=NR)}3CH(=NR)] derived from a successive insertion of isocyanide into the palladium-hydride bond of trans-[Pd(H)Cl(PPh(3))(2)] (2), which was generated from the reaction of 1 and H(2)SiMePh in situ. The pentaimino ligand attached to the metal through the carbon atom of the alpha-imino group and the lone pair electron of the gamma-imino nitrogen atom, resulting in a five-membered chelate ring. The reaction of 3 with XylNC in the presence of H(2)SiMePh afforded the heterobicyclic compound 4a. Similar treatments of 3 with 2,4,6-mesityl isocyanide (MesNC) and carbon monoxide (similar to 80 kg cm(-2)) in the presence of H(2)SiMePh gave 2,6-(2',6'-xylyl)(2)-3-(2',4',6'-mesitylimino)-7-(2',6'-xylylimino)-4,8-(2',6'-xylylamino)(2)-2,6-diazabicyclo[3.3.0]octa-4,8-diene (5) and 2,6-(2',6'-xylyl)(2)-7-(2',6'-xylylimino)-4,8-(2',6'-xylylamino)(2)-2,6-diazabicyclo[3.3.0]octa-4,8-dien-3-one (6), respectively. The structure of 6 was confirmed by X-ray crystallography. When complex 3 was treated with HC=CPh, a pyrrole compound, 1-(2',6'-xylylamino)-2-phenyl-4-R'-pyrrole (R' = C(=NR){C(=NR)}2CH(=NR), R = Xyl) (7), was obtained. The structure of 7 . C6H6 was confirmed by X-ray crystallography. Possible mechanisms for 4-7 were proposed., 1996年07月, ORGANOMETALLICS, 15 (15), 3404 - 3411, web_of_science

    研究論文(学術雑誌)

  • Asymmetrical A-frame triplatinum clusters bridged by small organic molecules and bis((diphenylphosphino)methyl)phenylphosphine

    T Tanase; H Ukaji; T Igoshi; Y Yamamoto

    Reactions of the linear triplatinum complex [Pt-3(mu-dpmp)(2)(XylNC)(2)](2+) (3) with small organic molecules led to formation of asymmetrical A-frame triplatinum complexes with an additional bridge across one of the metal-metal bonds, where dpmp is bis((diphenylphosphino)methyl)phenylphosphine. Reaction of complex 3 with electron deficient alkynes (R(1)C=CR(2): R(1) = R(2) = CO(2)Me; R(1) = H, R(2) = CO(2)Me; R(1) = R(2) = CO(2)Et) afforded a new series of triplatinum clusters formulated as [Pt-3(mu-dpmp)(2)(mu-R(1)CCR(2))(XylNC)(2)](PF6)(2) (5a, R(1) = R(2) = CO(2)Me; 5b, R(1) = H, R(2) = CO(2)Me; 5c, R(1) = R(2) = CO(2)Et) in good yields. The complex cation of 5b was characterized by X-ray crystallography to have an asymmetrical A-frame structure comprising three Pt atoms bridged by two dpmp ligands, in which an acetylene molecule was inserted into one of the Pt-Pt bonds (triclinic, <P(1)over bar>, a = 19.507-(3) Angstrom, b = 20.327(4) Angstrom, c = 14.499(4) Angstrom, alpha = 107.69(2)degrees, beta = 102.08(2)degrees, gamma = 71.30(1)degrees, V = 5148 Angstrom(3), Z = 2, R = 0.070, and R(w) = 0.084). The Pt-Pt bond length is 2.718(1) Angstrom and the Pt ... Pt nonbonded distance is 3.582(1) Angstrom. Treatment of 3 with an excess of HBF4 . Et(2)O gave the asymmetrical cluster [Pt-3(mu-dpmp)(2)(mu-H)-(XylNC)(2)](BF4)(3) . CH2Cl2 (6 . CH2Cl2), in 61% yield, and a similar reaction with p-NO2C6H4NC led to the formation of [Pt-3(mu-dpmp)(2)(mu-R(3)NC)(XylNC)(2)](PF6)(2) . CH2Cl2 (7 . CH2Cl2) in 94% yield (R(3) = p-NO2C6H4). Complexes 6 and 7 are assumed to have a single atom-bridged, asymmetrical A-frame structures. Reaction of the complex syn-[Pt-2(mu-dpmp)(2)(XylNC)(2)](2+) (1) With [MCl(2)(cod)] (M = Pt, Pd) gave the dimer-monomer combined trinuclear cluster [Pt(2)MCl(2)(mu-dpmp)(2)(XylNC)(2)](PF6)(2) (8a, M = Pt, 89%; 8b, M = Pd, 55 %). The structure of 8a was determined by X-ray crystallography to be comprised of a metal-metal-bonded diplatinum core and a monomeric platinum center bridged by two dpmp ligands with a face-to-face arrangement (triclinic, <P(1)over bar>, a = 18.082(7) Angstrom, b = 19.765(6) Angstrom, c = 15.662(4) Angstrom, alpha = 98.51(2)degrees, beta = 94.24(3)degrees, gamma = 109.82(2)degrees, V = 5161 Angstrom(3), Z = 2, R = 0.069, and R(w) = 0.080). The Pt-Pt bond length is 2.681(2) Angstrom and the Pt ... Pt nonbonded distance is 3.219(2) Angstrom. The heteronuclear complex 8b was transformed to an A-frame trinuclear cluster, [Pt2PdCl(mu-Cl)(mu-dpmp)(2)(XylNC)]-(PF6)(2) (9), which was characterized by X-ray crystallography (monoclinic, C2/c, a = 33.750(9) Angstrom, b = 28.284(9) Angstrom, c = 23.845(8) Angstrom, beta = 118.19(4)degrees, V = 20066 Angstrom(3), Z = 8, R = 0.082, and R(w) = 0.077). The diplatinum unit (Pt-Pt = 2.606(2) Angstrom) is connected to the mononuclear Pd center by a chloride bridge (Pt ... Pd = 3.103(3) Angstrom, Pt-Cl-Pd = 79.6(3)degrees)., 1996年07月, INORGANIC CHEMISTRY, 35 (14), 4114 - 4119, web_of_science

    研究論文(学術雑誌)

  • Zinc-containing carboxylate-bridged heterodimetallic complexes and their reactions with phosphodiester ligands

    T Tanase; JW Yun; SJ Lippard

    A series of zinc-containing heterodimetallic complexes were prepared by using the dinucleating ligand XDK [H(2)XDK = m-xylylenediamine bis(Kemp's triacid imide)]. Mononuclear [Zn(XDK)(H2O)] (1) reacts with 1 equiv of M(acac)(2) . 2H(2)O (acac = 2,4-pentanedionate) to afford the heterodimetallic compounds [Zn(II)M(II)(XDK)(acac)(2)(CH3OH)(2)]. H2O (2 . H2O, M = Co, 65% isolated yield; 3 . H2O, M = Mn, 54%; 4 . H2O, M Fe, 30%; 5 . H2O, M = Ni, 32%). As determined by X-ray crystallography, 2-5 each contain a Zn(II)M(II) dinuclear core bridged by XDK and acac ligands. The zinc and M atoms have trigonal bipyramidal and octahedral geometries, respectively. The Zn M separations depend on the metal ion in the octahedral site (2, M = Co, 3.440(2) Angstrom; 3, M = Mn, 3.517(1) Angstrom; 4, M = Fe, 3.492(1) Angstrom; 5, M = Ni, 3.397(1) Angstrom), a variation which is correlated with the ionic radius of the high-spin octahedral metal ion. The reaction of 2 with diphenyl hydrogen phosphate afforded the bis(phosphate) complex [ZnCo(XDK){mu-eta(2)-(PhO)(2)PO2},{eta(1)-(PhO)(2)PO2}(CH3OH)(2)(H2O)] (7, 49% yield). The ZnCo center is bridged by the XDK through its two carboxylate groups and by a diphenyl phosphate ligand. The other diphenyl phosphate is terminally coordinated to the zinc atom in a monodentate fashion. The Zn...Co interatomic distance is 3.846(1) Angstrom. An analogous bis(phosphate) homodinuclear complex, [Zn-2(XDK){mu-eta(2)-(PhO)(2)PO2},{eta(1)-(PhO)(2)PO2}(CH3OH)(2)(H2O)] (8), was prepared by reacting [Zn-2(XDK)(acac)(2)(CH3OH)(2)] (6) with diphenyl hydrogen phosphate in 64% yield. Compound 8, which is isomorphous with 7, has an asymmetrical dizinc core bridged by XDK and a phosphate ligand (Zn...Zn = 3.869(2) Angstrom). The monodentate diphenyl phosphate ligand dissociates from the dimetallic center of 8 in solution, as revealed by molar conductivity and H-1 and P-31{H-1} NMR spectroscopic studies. The resulting free phosphate ligand exchanges with the bridging one in methanol-d(4). The present results provide a useful synthetic route to carboxylate-bridged heterodimetallic compounds, which are potential models for the active centers in nonredox metalloproteins. Crystal data are as follows. 2: monoclinic, P2(1)/c, a = 17.725(7) Angstrom, b = 12.354(4) Angstrom, 21.815(6) Angstrom, beta = 90.45(3)degrees, V = 4777(2) Angstrom(3), Z = 4; R = 0.049 and R(w) = 0.051 for 3884 reflections with I > 3 sigma(I). 3: monoclinic, P2(1)/c, a 17.292(2) Angstrom, b = 12.450(1) Angstrom, c 21.717(2) Angstrom, beta = 91.464(7)degrees, V = 4673.9(7) Angstrom(3), Z = 4; R = 0.046 and R(w) = 0.051 for 3876 reflections. 4: monoclinic, P2(1)/c, a 17.630(1) Angstrom, b = 12.374(2) Angstrom, c = 21.771(2) Angstrom, beta = 90.306(8)degrees, V = 4749.4(7) Angstrom(3), Z = 4; R = 0.041 and R(w) 0.049 for 3248 reflections. 5: monoclinic, P2(1)/c, a 17.817(2) Angstrom, b = 12.241(3) Angstrom, c = 21.786(2) Angstrom, beta = 91.043(9)degrees, V = 4751(1) Angstrom(3), Z = 4; R = 0.050 and R(w) = 0.058 for 4497 reflections. 7 . CH3OH: monoclinic, P2(1)/n, a = 18.812(2) Angstrom(3), b = 16.156(2) Angstrom, c = 21.760(2) Angstrom, beta = 112. 836(9)degrees, V = 6095(1) Angstrom(3), Z = 4; R = 0.055 and R(w) = 0.064 for 5843 reflections. 8 . CH3OH: monoclinic, P2(1)/n, a 18.845(6) Angstrom, b = 16.105(3) Angstrom, c = 21.776(3) Angstrom, beta = 112.78(2)degrees, V = 6091(2) Angstrom(3), Z = 4; R = 0.055 and R(w) = 0.061 for 5189 reflections., 1996年06月, INORGANIC CHEMISTRY, 35 (12), 3585 - 3594, web_of_science

    研究論文(学術雑誌)

  • Clusters [{Pt(diphosphine)(isocyanide)}(2)Pt](2+) recharacterized as [{Pt(diphosphine)(isocyanide)}(2)Hg](2+)

    T Tanase; Y Yamamoto; RJ Puddephatt

    The clusters already reported as [{Pt(diphos)-(RNC)}Pt-2](PF6)(2), (diphos = cis-Ph(2)PCH=CHPPh(2), Ph(2)P(CH2)(3)PPh(2), or (t)Bu(2)P(CH2)(2)P(t)Bu(2); R = 2,6-xylyl or 2,4,6-mesityl) have been. recharacterized to be the Pt-Hg-Pt mixed-metal clusters [{Pt(diphos)(RNC)}Hg-2]-(PF6)(2) on the basis of metal analysis and the reevaluation of P-31{H-1} NMR spectra and X-ray crystallographic structures., 1996年03月, ORGANOMETALLICS, 15 (5), 1502 - 1504, web_of_science

    研究論文(学術雑誌)

  • Diruthenium(II)Complex with an Unprecedented S, O-Bidentate Bridge of Dimethyl Sulfoxide

    T. Tanase; T. Aiko; Y. Yamamoto

    1996年, Chem. Commun., 2341-2342

  • Syntheses of aromatic bridged cryptophanes and their complexing abilities with alkyl ammonium cations

    M Miura; S Yuzawa; M Takeda; M Takeda; Y Habata; T Tanase; S Akabori

    Several aromatic bridged cryptophanes were successfully synthesized. p-Xylene bridged cryptophane Anti-3 was prepared by the direct trimerization of alpha,alpha'-bis[4-hydroxymethyl-2-methoxyphenoxy]-p-xylene. The synthesis of o-xylene bridged cryptophane Anti-8 was carried out by the direct trimerization and/or the stepwise method from vanillyl alcohol. The o-[4,5-bis(methoxycarbonyl)]xylene bridged cryptophanes Anti-15a and Syn-15b were also prepared by the stepwise method from vanillyl alcohol. Anti-3 was capable of complexing with almost all the quaternary alkylammonium cations among the primary, secondary, tertiary and quaternary ammonium cations, and selectively prefered to complex with the NEt(3)Me(+) cation as a guest. From the complexation of the o-xylene bridged cryptophanes Anti-8, and the analogs Anti-15a and Syn-15b with the NMe(4)(+) cation, the cryptophanes Anti-8 and Syn-15b were confirmed to complex with the guest cation, however, Anti-15a was not confirmed to be included., 1996年, SUPRAMOLECULAR CHEMISTRY, 8 (1), 53 - 66, web_of_science

    研究論文(学術雑誌)

  • Intelligent sugar complexes

    S Yano; M Nakagoshi; A Teratani; M Kato; T Tanase; Y Yamamoto; H Uekusa; Y Ohashi

    The structure of [Co((Rha)(3)-tren)]Br-2.2CH(3)OH, where (Rha)3-tren is tris (N-rhamnosyl-2-aminoethyl)amine, was elucidated by X-ray crystallography, which confirmed the unprecedented configurational inversion of [Co((Rha)(3)-tren)](2+), around the metal center reversibly by an addition and a removal of sulfate., 1996年, MOLECULAR CRYSTALS AND LIQUID CRYSTALS SCIENCE AND TECHNOLOGY SECTION A-MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 276, 253 - 256, web_of_science

    研究論文(学術雑誌)

  • Successful Isolation of an Intermediate to [Ni(aldose3-tren)]2+ (aldose3-tren=tris(N-aldosy-2-aminoethyl)amine : X-Ray Crystal Structure of {Tris(N-L-rhamnosyl-2-aminoethyl)amine)(sulfate)nickel(II)Hydrate Trime

    TANASE Tomoaki; S. Yano; M. Doi; M. Kato; I. Okura; T. Nagano; Y. Yamamoto; T. Tanase

    1996年, Inorg. Chem. Acta, 249, 1-3

  • LABILE COORDINATION OF BIS(DIPHENYLPHOSPHINOMETHYL) PHENYLPHOSPHINE IN DINUCLEAR AND TRINUCLEAR PALLADIUM AND PLATINUM COMPLEXES CONTAINING ORTHO-SUBSTITUTED AROMATIC ISOCYANIDE

    Y YAMAMOTO; T TANASE; H UKAJI; M HASEGAWA; T IGOSHI; K YOSHIMURA

    Reaction of [Pd-2(RNC)(6)](2+) with (Ph(2)PCH(2)),PPh (dpmp) gave [Pd-2(dpmp)(2)(RNC)(2)](2+) 1, in which dpmp ligands acted as chelating ligands. Thermal reaction of 1 underwent an elimination of isocyanide and change of a coordination mode of the dpmp ligands to give [Pd-2(dpmp)(2)(RNC)](2+) 2. Two kinds of new dimeric complexes [Pt-2(dpmp)(2)(RNC)(2)](2+) (4, 5) were obtained from [Pt-2(RNC)(6)](2+) and dpmp, in which dpmp ligands acted as bi- and tridentate ligand to bridge a metal-metal bond. Compounds 4 and 5 are interconvertible. Reaction of 5 with M(3)(RNC)(6) (M = Pt, Pd) gave a linear home- or hetero trinuclear complex, [Pt(2)M(dpmp)(2)(RNC)(2)](2+) (6, 7)., 1995年08月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 498 (1), C23 - C26, web_of_science

  • Dinuclear Manganese(II)Complexes with the {Mn2(μ-carboxtlato)2}+ Core and Their Transformation to (μ-Oxo)bis(μ-carboxylato)dimanganese(III) Complexes

    T TANASE; SJ LIPPARD

    Dinuclear Mn(II) complexes having a substitutionally labile {Mn-2(mu-carboxylato)(2)}(2+) core were readily synthesized by using the dinucleating ligand XDK, where H(2)XDK = m-xylenediamine bis(Kemp's triacid imide). Reaction of Mn(NO3)(2) . 6H(2)O With Na(2)XDK .4H2O resulted in quantitative formation of [Mn-2(XDK)(NO3)(CH3OH)(4)(H2O)(2)]-(NO3) (1), which was characterized by X-ray crystallography (monoclinic, P2(1)/c, a = 11.226(1) Angstrom, b = 13.120-(1) Angstrom, c = 30.467(3) Angstrom, beta = 98.739(8)degrees, V = 4435.2(7) Angstrom(3), Z = 4, and R = 0.034 and R(w) = 0.045 for 4957 independent reflections with I > 3 sigma(I)). The cation in 1 contains two octahedral Mn(II) ions bridged by the two carboxylate groups of XDK (Mn...Mn = 4.8497(7) Angstrom), the terminal positions being occupied by labile solvent molecules and a nitrate anion. Compound 1 proved to be a good precursor for preparing a series of bis(mu-carboxylato)dimanganese(II) complexes with N-donor bidentate terminal ligands. Reaction of 1 with 2,2'-dipyridyl (bpy), 4,4'-dimethyl-2,2'-dipyridyl (4,4'-Me(2)bpy), or 1,10-phenanthroline (phen) afforded [Mn-2(XDK)-L(2)(NO3)(2)(H2O)] (L = bpy (2), 4,4'-Me(2)bpy (3), or phen (4)) in high yields. The structure of 2 . CH2Cl2 was shown by X-ray crystallography to have an asymmetric dinuclear Mn(II) core bridged by XDK with a Mn...Mn distance of 4.557(2) Angstrom. One Mn(II) atom adopts an octahedral geometry while the other has a distorted trigonal bipyramidal environment (monoclinic, P2(1)/c, a = 14.491(2)Angstrom b = 17.954(2) Angstrom c = 22.492(3) Angstrom, beta = 108.787-(9)degrees, V = 5537(1) Angstrom(3), Z = 4, and R = 0.055 and R(w) = 0.058 for 4438 independent reflections with I > 3 sigma(I)). Compounds 2 and 3 are readily oxidized by excess tert-butyl hydroperoxide in methanol to afford (mu-oxo)bis(mu-carboxylato)dimanganese(III) complexes, [Mn-2(mu-O)(XDK)L(2)(NO3)(2)] (L = bpy (5) and 4,4'-Me(2)bpy (6)). The crystal structure of 6 . 2.5CH(3)OH revealed two octahedral Mn(III) ions symmetrically bridged by two carboxylate groups of XDK and an oxo ligand. The metal-metal separation is 3.170(2) Angstrom, and the two 4,4'-Me(2)bpy ligands lie in anti arrangement with respect to the Mn-O-Mn plane (orthorhombic, Pbcn, a = 41.636(9) Angstrom, b = 13.108-(1) Angstrom, c = 22.422(9) Angstrom, V = 12237(2) Angstrom(3), Z = 8, and R = 0.073 and R(w), = 0.085 for 3731 independent reflections with I > 3 sigma(I)). Complexes 5 and 6 could be prepared in low yields by air oxidation of 2 and 3, respectively, a reaction that was readily reversed by treatment with hydrogen peroxide. Reaction of 2-4 with an excess amount of hydrogen peroxide quite slowly evolved dioxygen, whereas the solvento dimanganese(II) compound 1 efficiently disproportionated hydrogen peroxide by first converting to a heterogeneous catalyst. A mononuclear complex, [Mn(HXDK)(2)(H2O)(2)] (7), prepared independently, and MnO2 were isolated from the heterogeneous mixture, and the latter was shown to be the active species for disproportionating hydrogen peroxide., 1995年08月, INORGANIC CHEMISTRY, 34 (18), 4682 - 4690, web_of_science

    研究論文(学術雑誌)

  • MONONUCLEAR AND DINUCLEAR ZINC-COMPLEXES OF XDK, H(2)XDK=M-XYLENEDIAMINE BIS(KEMP TRIACID IMIDE), AND THEIR REACTION WITH PHOSPHATE-ESTERS

    T TANASE; JW YUN; SJ LIPPARD

    The reaction of Zn(NO3)(2) . 6H(2)O with H(2)XDK and NaOH afforded the mononuclear zinc complex, [Zn(XDK)-(H2O] (1), in good yield. Treatment with pyridine converted complex 1 to [Zn(XDK)(py)(2)]. H2O (2 . H2O), which was characterized by X-ray crystallography (2 . CHCl3: monoclinic, P2(1)/c, a 12.324(4) Angstrom, b = 14.902(3) Angstrom c = 24.674(5) Angstrom, beta = 102.86(3)degrees, V = 4418(2) Angstrom(3), Z = 4, and R = 0.088 and R(w) = 0.089 for 3833 independent reflections having I > 3 sigma(I)). Complex 2 has two Zn-O and two Zn-N bonds at average distances of 2.04 and 2.07 Angstrom, respectively, contributed by a distorted XDK and two pyridine ligands. There is also a longer interaction to a third oxygen atom of the XDK ligand, Zn-O = 2.39 Angstrom. Recrystallization of 2 . H2O from a methanol/pyridine mixed solvent gave {Zn(eta(1)-carboxylato)(2)(py)(2)} (2'), which was isolated and structurally characterized (2'. CH3OH: monoclinic, P2(1)/n, a 12.257(2) Angstrom, b = 16.448(2) Angstrom, c = 20.432(3) Angstrom, beta = 103.46(1)degrees, V = 4006.0(9) Angstrom(3), Z = 4, and R = 0.048 and R(w) = 0.054 for 4140 independent reflections with I > 3 sigma(I)). Complex 1 readily reacted with Zn(NO3)(2) . 6H(2)O to give the dizinc complex, [Zn-2(XDK)(NO3)(2)(CH3OH)(H2O)(2)] (3), and a similar reaction in the presence of pyridine gave [Zn-2(XDK)(py)(2)(NO3)(2)]. 2H(2)O (4 . 2H(2)O). Complex 4 was characterized by X-ray crystallography (4 . CH(2)Cl(2)Et(2)O: monoclinic, P2(1)/n, a = 17.938(3) (A)ngstrom, b = 21.232(4) Angstrom, c = 15.436(3) Angstrom, beta = 112.48(1)degrees, V = 5432(2) Angstrom(3), Z = 4, and R = 0.072 and R(w) = 0.082 for 3590 independent reflections with I > 3 sigma(I)). The Zn ... Zn separation is 3.739(2) Angstrom, and both zinc atoms adopt a tetrahedral geometry. When complex 1 was treated with Zn(acac)(2) .2H2O, the asymmetrical dinuclear zinc complex, [Zn-2(XDK)(acac)(2)(CH3-OH)(2)]. H2O (5 . H2O), was obtained in good yield. An X-ray crystallographic analysis revealed a dizinc structure bridged by XDK and acac ligands; one zinc atom has trigonal bipyramidal geometry, and the other, octahedral geometry. The Zn ... Zn interatomic distance is 3.463(1) Angstrom (5: monoclinic, P2(1)/c, a = 17.629(3) Angstrom, b = 12.373(1) Angstrom, c 21.731(4) Angstrom, beta = 90.11(2)degrees, V = 4740(1) Angstrom(3), Z = 4, and R = 0.049 and R(w) = 0.054 for 5137 independent reflections with I > 3 sigma(I)). Reaction of complex 3 with phosphate ester salts NaC{RO)(2)PO2}, R = Ph or p-NO2-Ph, yielded the phosphate-bridged dinuclear zinc complexes, [Zn-2(XDK){mu-(RO)(2)PO2}(CH3OH)(2)](NO3) (6a, R = Ph; 6b, R = p-NO(2)Ph), which were further transformed into [Zn-2(XDK)mu-{RO)(2)PO2}(py)(2)(NO3) (7a, R = Ph; 7b, R = p-NO(2)Ph) by treatment with pyridine. These phosphate ester-bridged dizinc compounds are structural models for postulated intermediates in the mechanism proposed for phosphate ester hydrolysis by Escherichia coli alkaline phosphatase and DNA polymerase I, both of which contain a pair of zinc atoms in their active sites., 1995年08月, INORGANIC CHEMISTRY, 34 (16), 4220 - 4229, web_of_science

    研究論文(学術雑誌)

  • Syntheses and Characterization of Diruthenium(III) Alky-alkyl and Alkyl-alkynyl Complexes with two Bridging Thiolate Ligands [Cp*Ru(R(μ-SPri)2-RuCp*R']Cp*5-C5Me5). X

    A TAKAHASHI; Y MIZOBE; T TANASE; M HIDAI

    Reactions of diruthenium alkyl-halido complexes containing two bridging thiolate ligands [Cp*RuR(mu-SPri)(2)RuCp*X](1; Cp* = eta(5)-C(5)Me(5), R = PhCH(2)CH(2), X = Br, R = Me, X = I) with R'MgX(R' = PhCH(2)CH(2), X = Br; R' = PhCH(2), X = Cl) or R'Li(R'= Me, PhC = C) in THF at room temperature afforded novel diruthenium alkyl-alkyl and alkyl-alkynyl complexes [Cp*RuR(mu-SPri)(2)RuCp*R'] (2). In contrast, treatment of 1a (R = PhCH(2)CH(2), X = Br) with EtMgBr resulted in the formation of an alkyl-hydrido complex [Cp*Ru(CH(2)CH(2)Ph)(mu-SPri)(2)RuCp*H] as the only isolable product. X-ray analysis of 2a (R = R'= PhCH(2)CH(2)) has disclosed the structure as consisting of the two Cp*Ru(CH(2)CH(2)Ph) units connected by two mu-SPri ligands together with a Ru-Ru single bond, in which the two alkyl groups are oriented mutually cis. Crystal data for 2a: monoclinic, space group P2(1)/c(No. 14) with a = 19.449(3) Angstrom, b = 10.210(3) Angstrom, c = 20.254(2) Angstrom, beta = 94.684(9)degrees, V = 4008(2) Angstrom(3), Z = 4, and R(R(W)) = 0.054 (0.041) for 2635 reflections [I > 3 sigma(I)]. Treatment of 2a with two equivalents of I-2 in THF resulted in the formation of PhCH(2)CH(2)I and [Cp*RuI(mu-SPri)(2)RuCp*I] (7c) as the major products, while treatment with 1.2 equivalents of I-2 afforded a mixture of Ph(CH2)(4)Ph and PhCH(2)CH(2)I along with 7e and unidentified Ru species., 1995年06月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 496 (1), 109 - 115, web_of_science

    研究論文(学術雑誌)

  • STUDIES ON THE INTERACTION OF ISOCYANIDE WITH TRANSITION-METAL COMPLEXES .41. NOVEL OXO-BRIDGED DINUCLEAR MOLYBDENUM(II) COMPLEXES - REACTION OF [MO-2(O2CCH3)(2)(CH3CN)(6)](BF4)(2) WITH AROMATIC ISOCYANIDES - X-RAY CRYSTAL-STRUCTURES OF [MO-2(MU-O)(RNC)(10)](BF4)(2) (R=2,6-ME(2)C(6)H(3)) AND [MO(=O)F(RNC)(4)](BF4) (R=2,4,6-ME(3)C(6)H(2))

    T IGOSHI; T TANASE; Y YAMAMOTO

    Treatment of the dinuclear molybdenum complex [Mo-2(O2CCH3)(2)(CH3CN)(6)](BF4)(2) with aromatic isocyanides (RNC) gave an ore-bridged dinuclear molybdenum(II) complex, [Mo2(mu-O)(RNC)(10)](BF4)(2) (1), and a mononuclear molybdenum(IV) complex, [Mo(= O)F(RNC)(4)]BF4(2) (R = 2,6-dimethylphenyl (Xyl) or 2,4,6-trimethylphenyl (Mes)), which were characterized by IR, electronic, H-1 and F-19 NMR spectroscopy and X-ray crystallographic analyses. Complex 1a (R = Xyl) crystallizes in the triclinic form, space group P (1) over bar, with a = 13.431(5) Angstrom, b = 15.548(7) Angstrom, c = 12.616(5) Angstrom, alpha = 111.74(3)degrees, beta = 92.80(3)degrees, gamma = 101.80(3)degrees and Z = 1 (R = 0.060 and R(w) = 0.054 for 2818 independent reflections with I > 3 sigma(I)). Complex 2b (R = Mes) crystallizes in the triclinic form, space group P (1) over bar, with a = 14.317(4) Angstrom, b = 16.16(1) Angstrom, c = 8.968(8) Angstrom, alpha = 100.31(4)degrees, beta = 97.54(2)degrees, gamma = 91.69(4)degrees and Z = 2 (R = 0.059 and R(w) = 0.059 for 2225 independent reflections with I > 3 sigma(l)). Complex 1 consists of two molybdenum atoms bridged linearly by an oxygen atom. Each molybdenum atom is octahedrally coordinated by five isocyanides and an oxygen atom. Two equatorial planes, Mo(RNC)(4), mutually adopt an eclipsed form. The Mo-O bond length is 1.876(2) Angstrom and the Mo-O-Mo angle is constrained to 180 degrees. Complex 2 has a distorted octahedral geometry, in which molybdenum atom is occupied by four isocyanides, O and F atoms., 1995年05月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 494 (1-2), 37 - 42, web_of_science

    研究論文(学術雑誌)

  • CARBOXYLATE-BRIDGED AND PHOSPHODIESTER-BRIDGED DINUCLEAR MAGNESIUM(II) COMPLEXES

    JW YUN; T TANASE; LE PENCE; SJ LIPPARD

    1995年04月, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 117 (15), 4407 - 4408, web_of_science

  • Novel Oxo-bridged Dinuclear Molybdenum(II) Complex : Reaction of [Mo2(O2CCH3)2(CH3CN)6](BF4)2 with Aromatic Isocyanides. X-Ray Crystal Structures of [Mo2(μ-

    TANASE Tomoaki; T. Igoshi; T. Tanase; Y. Yamamoto

    1995年, J. Organomet. Chem., 494, 37-42

  • Preparation of [Ruη6-C6Me6)Cl(CCPh)(RNC)](R=C8H9 or C6H2Me3-2,4,6)and its Reaction with Tetracyanoethylene. Crystal Structures of [Ru(η6-C6Me

    Y YAMAMOTO; R SATOH; T TANASE

    Reaction of [Ru(eta(6)-C(6)Me(6))Cl-2(RNC)] with phenylacetylene in the presence of potassium hydroxide in methanol gave the corresponding acetylide complex [Ru(eta(6)-C(6)Me(6))Cl(C=CPh)(RNC)] (R = C8H9 1a or 2,4,6-Me(3)C(6)H(2) 1b). Compound la reacted with triphenylphosphine at reflux in toluene to give [RU(eta(6)-C(6)Me(6))Cl(C=CPh)(PPh(3))] 2 and [RUCl(C=CPh)(C8H9NC)(PPh(3))] 3. When 1a was treated with tetracyanoethylene (tcne) at room temperature [Ru(eta(6)-C(6)Me(6))Cl{C[=C(CN)(2)]CPh=C(CN)(2)}(C8H9NC)] 4 was obtained. The structure was confirmed by an X-ray analysis: space group Pbca, a = 20.128(4), b = 17.821(6), c = 17.407(9) Angstrom, and Z = 8. The molecule contains a ligand resulting from alpha,beta addition. of C(CN)(2) fragments to the acetylide group. Reaction of 2 with tcne gave [RU(eta(6)-C(6)Me(6))Cl{C(CN)(2)CPhC=C(CN)(2)}] 5 which has lost the terminal isocyanide in 4. Preparation and X-ray analysis of square-planar cis-[RuCl2(C8H9NC)(2)] were also carried out: space group P ($) over bar 1, a = 10.573(3), b = 10.865(3), c = 8.244(2) Angstrom, alpha = 99.66(2), beta = 93.37(2). gamma = 85.85(3)degrees and Z = 2. The structure consists of a pair of molcules of cis configuration with a centrosymmetry, but there is no interaction between the ruthenium atoms., 1995年01月, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (2), 307 - 311, web_of_science

    研究論文(学術雑誌)

  • STUDIES ON INTERACTION OF TRANSITION-METAL COMPLEXES WITH ISOCYANIDES .40. REACTIONS OF DICOBALT OCTA(ISOCYANIDE) WITH 2-BROMOACETOPHENONE

    Y YAMAMOTO; T TANASE; K SUGANO

    The reaction of Co-2(XylNC)(8) (Xyl = 2,6-Me(2)C(6)H(3)) with 2-bromoacetophenone gave 2,3-bis(2,6-xylyl)imino-5-phenyl-2,3-dihy- drofuran (1a) and the cobalta-azacyclopentane derivative CoBr(PhCOCH)(XylNC)(6) (2a). Structures of 1a and 2a were determined by X-ray analyses; la is a furan derivative and 2a has a distorted octahedral structure containing a five-membered metallacyclic moiety formed by an multiple insertion of isocyanide into a Co-C bond. Similar treatment at reflux in the presence of xylyl isocyanide gave two kinds of octahedral compounds, 3a and 4a, having similar formula composition CoBr(PhCOCH)(XYINC)(5); 3a was found by X-ray analysis to have a cobaltacycle structure, containing a tridentate ligand consisting of sigma carbon, carbene and O-coordination sites, and 4a was proposed to have a cobalta-azacyclobutane framework., 1995年01月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 486 (1-2), 21 - 29, web_of_science

    研究論文(学術雑誌)

  • STEPWISE INCORPORATION OF ALKYNES INTO A COORDINATIVELY UNSATURATED DIRUTHENIUM CENTER BRIDGED BY THIOLATE LIGANDS

    M NISHIO; H MATSUZAKA; Y MIZOBE; T TANASE; M HIDAI

    The coordinatively unsaturated complex Cp*Ru(mu(2)-SPri)(2)RuCp* (1; Cp* = eta(5)-C(5)Me(5)) readily reacts with an equimolar amount of HC=CCO(2)R (R = Me, Et, Bu(t)) at the diruthenium center to give dinuclear complexes with a ruthenathiacyclobutene core, Cp*Ru(mu(2)-SPri)[eta(2):eta(2)-mu(2)-C(CO(2)R)=CHSPri]RuCp* (5a, R = Me; 5b, R = Et; 5c, R = Bu(t)). Subsequent treatment of 5a with the series of alkynes HC=CR' (R' = CO(2)Me, Tol, SiMe(3); Tol = 4-MeC(6)H(4)) results in the incorporation of another alkyne molecule into the diruthenium site in 5a, affording either dinuclear ruthenacyclopentenyl complexes Cp*Ru(mu(2)-SPri)[eta(2):eta(3)-mu(2)-C(R')CHC(CO(2)Me)CHSPri]RuCp* (6a, R' = CO(2)Me; 6b, R' = Tol) or the bridging alkyne complex Cp*Ru(mu(2)-SPri)(mu(2)-H)[eta(2): eta(2)-mu(2)-R'C=CC(CO(2)Me)=CHSPri]RuCp* (7; R' = SiMe(3)). From 6, two types of dinuclear ruthenacyclopentadiene complexes are obtained by the reactions with Mel: the neutral diiodo complex Cp*I2Ru[eta(2):eta(4)-mu(2)-C(CO(2)Me)CHC(CO(2)Me)CH]RuCp* (8) from 6a and the cationic complex [Cp*Ru(mu(2)-SPri){eta(2):eta(4)-mu(2)-C(Tol)CHC(CO(2)Me)CH}RuCp*]I (10a) from 6b. A dimethyl analogue of 8, Cp*Me(2)Ru[eta(2):eta(4)-mu(2)-C(CO(2)Me)CHC(CO(2)Me)CH]RuCp* (9), is further derived from 8 upon treatment with LiCuMe(2). On the other hand, oxidation of the alkyne complex 7 with I-2 results in the release of the coordinated alkyne Me(3)SiC=CC(CO(2)Me)=CHSPri (11). Structures of 5c, 6a, 7, 9, and 10b (PF6- salt of the cation in 10a) have been unambiguously established by X-ray diffraction studies. Crystal data: 5c, triclinic, P $$($) over bar 1, a = 11.2375(9) Angstrom, b = 17.876(4) Angstrom, c = 9.079(2) Angstrom, alpha = 94.70(3)degrees, beta = 105.54(1)degrees, gamma = 92.01(1)degrees, Z = 2, 5596 reflections, R = 0.051, R(w) = 0.058; 6a, triclinic, P $$($) over bar 1, a = 10.999(3) Angstrom, b = 19.155(4) Angstrom, c = 9.139(2) Angstrom, alpha = 102.22(1)degrees, beta = 107.96(2)degrees, gamma = 78.28(2)degrees, Z = 2, 5448 reflections, R = 0.045, R(w) = 0.057; 7, triclinic, P $$($) over bar 1, a = 11.323(3) Angstrom, b = 17.356(3) Angstrom, c = 10.627(2) Angstrom, alpha = 101.80(1)degrees, beta = 109.79(2)degrees, gamma = 80.78(2)degrees, Z = 2, 2352 reflections, R = 0.079, R(w) = 0.051; 9, orthorhombic, P2(1)2(1)2(1), a = 16.412(5) Angstrom, b = 16.650(6) Angstrom, c = 10.594(3) Angstrom, Z = 4, 1956 reflections, R = 0.049, R(w) = 0.036; 10b.ClCH2CH2Cl, triclinic, P $$($) over bar 1, a = 12.537(2) Angstrom, b = 18.442(2) Angstrom, c = 9.2737(9) Angstrom, alpha = 95.105(9)degrees, beta = 96.545(9)degrees, gamma = 94.81(1)degrees, Z = 2, 5103 reflections, R = 0.068, R(w) = 0.088., 1994年11月, ORGANOMETALLICS, 13 (11), 4214 - 4226, web_of_science

    研究論文(学術雑誌)

  • PREPARATION OF 1,1'-BIS[(DIPHENYLPHOSPHINO)METHYL]FERROCENE AND ITS TRANSITION-METAL COMPLEXES

    Y YAMAMOTO; T TANASE; MORI, I; Y NAKAMURA

    1,1'-Bis[(diphenylphosphino)methyl]ferrocene (dpmf), prepared from 1,1'-bis(chloromethyl)ferrocene and LiPPh2, reacted with [PdCl2(MeCN)2] to give [Pd2Cl2(dpmf2] 1, and treatment of 1 with [Pd3(2,6-Me2C6H3NC)6] in a 1 : 0.66 ratio in the presence of NH4PF6 and 2,6-Me2C6H3NC produced a macrocyclic complex [Pd4(2,6-Me2C6H3NC)8(dpmf)2]4+., 1994年11月, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (21), 3191 - 3192, web_of_science

  • CARBOXYLATE-BRIDGED HETERODIMETALLIC COMPLEXES

    T TANASE; SP WATTON; SJ LIPPARD

    1994年10月, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 116 (20), 9401 - 9402, web_of_science

  • Synthesis and Characterization of (n-Alkoxo)bis(n-carboxylato)diruthenium Complexes, Na[Ru2(dhpta)(n-O2CR)2](dhptaH5=1,3-diamino-2-hydroxypropane tetraacetic acid).

    T.Tanase; M.Kato; Y.Yamada; K.Tanaka; K.Lee; Y.Sugihara

    The first ruthenium analogue of hemerythrin models with CL-alkoxo bridging, Na[Ru(dhpta)(mu O(2)CR)(2)] (1:R = CH3, 2:R = C6H5, 3:R = C6H4-p-OH, 4:R = C6H4-p-NH2) have been prepared and characterized, and the crystal structure of 1 has been determined; these compounds undergo two one-electron reductions to the (RuRuIII)-Ru-II and (RuRuII)-Ru-II states with large separations (similar to 0.6 V) between the successive redox potentials, allowing the formation of stable mixed-valence species., 日本化学会, 1994年09月, Chem. Lett., (10), 1853 - 1856, web_of_science

    研究論文(学術雑誌)

  • SYNTHESES OF MIXED-METAL SULFIDE CUBANE-TYPE CLUSTERS WITH THE NOVEL PDMO3S4 CORE AND REACTIVITIES OF THE UNIQUE TETRAHEDRAL PD SITE SURROUNDED BY SULFIDE LIGANDS TOWARD ALKENES, CO, (T)BUNC, AND ALKYNES

    T MURATA; Y MIZOBE; H GAO; Y ISHII; T WAKABAYASHI; F NAKANO; T TANASE; S YANO; M HIDAI; ECHIZEN, I; H NANIKAWA; S MOTOMURA

    An incomplete cubane-type cluster [Mo3S4(H2O)(9)]Cl-4 (1) reacted with Pd black in aqueous HCl to give a mixed-metal cubane-type cluster [PdMo3S4(H2O)(9)Cl]Cl-3 (2). Treatment of 2 with 3.3 equiv of 1,4,7-triazacyclononane (tacn) afforded a well-defined single cubane-type cluster [PdMo3S4(tacn)(3)Cl]Cl-3 (3), while an anion metathesis of 2 by 4-toluenesulfonate (TsO) resulted in the formation of a double cubane-type cluster [Pd2Mo6S8(H2O)(18)] (OTs)(8) (4). Detailed structures of both 3 and 4 have been determined by X-ray crystallography. Crystal data for 3.4H(2)O: orthorhombic, space group P2(1)2(1)2(1), a = 17.549(3) Angstrom, b = 20.032(4) Angstrom, c = 10.256(2) Angstrom, V = 3605 Angstrom(3), Z = 4, and R (R(w)) = 0.051 (0.062) for 4014 reflections. For 4.24H(2)O: triclinic, space group P1, a = 15.799(4) Angstrom, b = 18.079(6) Angstrom, c = 11.873(1) Angstrom, alpha = 108.75(2)degrees, beta = 108.73(1)degrees, gamma = 70.87(3)degrees, V = 2944 Angstrom(3), Z = 1, R (R(w)) = 0.028 (0.036) for 10 089 reflections. Cluster 3 was converted into a series of single cubane-type clusters [PdMo3S4(tacn)(3)(L)](4+) containing alkenes, CO, and (t)BuNC coordinated to the tetrahedral Pd site, by the initial anion exchange forming [PdMo3S4(tacn)(3)Cl]X(3) (8a, X = ClO4; 8b, X = BF4; 8c, X = PF6) followed by treatment with these molecules. The alkene cluster [PdMo3S4(tacn)(3)(cis-HOCH2CH=CHCH2OH)](ClO4)(4) (5a') and the carbonyl cluster [PdMo3S4(tacn)(3)(CO)]Cl(ClO4)(3) (6a) have been fully characterized by X-ray analyses. Crystal data for 5a'.2H(2)O: monoclinic, space group P2(1)/m, a = 12.314(1) Angstrom, b = 12.732(2) Angstrom, c = 15.736(2) Angstrom, beta = 94.01(1)degrees, V = 2461 Angstrom(3), Z = 2, R (R(w)) = 0.068 (0.081) for 2743 reflections. For 6a.3H(2)O: orthorhombic, space group Pbca, a = 15.485(13) Angstrom, b = 23.900(6) Angstrom, c = 23.326(7) Angstrom, V = 8633 Angstrom(3), Z = 8, and R (R(w)) = 0.061 (0.069) for 7761 reflections. Interestingly, cluster 8c catalyzes the reaction of a series of alkynic acid esters R(2)C-CCOOR(1) with alcohols R(3)OH to give the trans addition products (Z)-(R(3)O)R(2)C=CHCOOR(1) (R(1) = Me, Et, (t)Bu, Ph, R(2) = H, R(3) = Me; R(1) = R(3) = Me, R(2) = COOMe, Me; R(1) = Ph, R(2) = Et, R(3) = Me; R(1) = Me, R(2) = H, R(3) = Et, PhCH(2)) with quite high selectivity under mild conditions with retention of the cluster core., 1994年04月, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 116 (8), 3389 - 3398, web_of_science

    研究論文(学術雑誌)

  • ELECTROCHEMICAL PREPARATION OF PLATINUM ISOCYANIDE CLUSTERS CONTAINING CHELATING DIPHOSPHINES - AN UNPRECEDENTED TRINUCLEAR PLATINUM COMPLEX INVOLVING A COORDINATIVELY UNSATURATED METAL CENTER, [(PT(DIPHOSPHINE)(ISOCYANIDE))2PT](PF6)2

    T TANASE; H UKAJI; Y KUDO; M OHNO; K KOBAYASHI; Y YAMAMOTO

    A controlled-potential electrolysis was performed on mononuclear platinum(II) complexes containing aromatic isocyanide (RNC) and diphosphine (diphos) ligands, [Pt(diphos)((RNC)2](PF6)2 diphos = cis-1,2-bis(diphenylphosphino)ethene (dppen) (1), 1,2-bis(diphenylphosphino)ethane (dppe) (2),1,3-bis(diphenylphosphino)propane (dppp) (3),1,4-bis(diphenylphosphino)butane (dppb) (4), and 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) (5); R = 2,6-dimethylphenyl or 2,4,6-trimethylphenyl), which were derived from the reaction of PtCl2(COD) with diphos, RNC, and NH4PF6. Electrolyses of complexes 1-4 at a mercury-pool electrode consumed 1 F mol-1 in acetonitrile at -1.45 to -1.5 V (vs Cp2Fe/CP2Fe+), which gave dinuclear platinum(I) complexes, [Pt4(diphos)2(RNC)2] (PF6)2 (diphos = dppen (6), dppe (7), dppp (8), and dppb (9)). The compounds were characterized by IR, electronic, and H-1 and P-31{H-1} NMR spectroscopy and X-ray crystallographic and EXAFS (extended X-ray absorption fine structure) analyses. Complex 8b (R = 2,4,6-Me3C6H2, diphos = dppp) crystallizes in the monoclinic system, space group P2(1)/c, with a = 14.941(4) angstrom, b = 19.268(6) angstrom, c = 26.002(9) angstrom, beta = 101.23(2)degrees, and Z = 4 (R = 0.059 and R(w) = 0.051 for 5704 independent reflections with I > 3sigma(I)). Complex 8b consists of two platinum atoms, each coordinated by one isocyanide, one diphosphine as a chelating ligand, and the neighboring platinum atom in a square planar array. The length of the Pt-Pt bond is 2.653(1) angstrom. EXAFS analyses showed that the Pt-Pt bond lengths of 6-9 fall within the narrow range of 2.625-2.653 angstrom. Electrolyses of 1, 3, and 5 consumed 1.5 F mol-1 at ca. -1.8 V, which gave trinuclear platinum complexes, [{Pt(diphos)(RNC)}2Pt](PF6)2 (diphos = dppen (13), dppp (14), and dtbpe (15)). Complex 13a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group P2/n, with a = 14.956(4) angstrom, b = 12.395(2) angstrom, c = 22.923(7) angstrom, beta = 104.35(2)degrees, and Z = 2 (R = 0.048 and R(w) = 0.046 for 2872 independent reflections with I > 3sigma(I)); complex 14a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group P2(1), with a = 15.491(3) angstrom, b = 22.575(5) angstrom, c = 10.883(3) angstrom, beta = 107.48(2)degrees, and Z = 2 (R = 0.056 and R(w) = 0.038 for 3156 independent reflections with I > 3sigma(I)); and complex 15a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group C2/c, with a = 19.489(6) angstrom, b = 15.284(5) angstrom, c = 25.804(6) angstrom, beta = 116.34(2)degrees, and Z = 4 (R = 0.045 and R(w) = 0.033 for 2904 independent reflections with I > 3sigma(II). The three platinum atoms were arranged in a linear array with Pt-Pt bond distances of 2.615(1) angstrom (13a), average 2.640 angstrom (14a), and 2.6409(8) angstrom (15a). The outer Pt atoms are coordinated by one isocyanide and one chelating diphosphine, and the central Pt atom is bound only to the two neighboring Pt atoms, resulting in a coordinatively unsaturated platinum center. The coordinatively unsaturated triplatinum complexes 13-15 have 40 valence electrons and are extremely electron-deficient. In the electrolysis of 5a, further reduction led to the formation of a mononuclear hydride complex of platinum, [PtH(dtbpe)-(2,6-Me2C6H3NC)]PF6 (16a). The potentiostatic electrolysis of 2 consumed 1. 5 F mol-1 to afford the coordinatively saturated triplatinum complex, [{Pt(dppe)(RNC)}2Pt(RNC)2](PF6)2 (10), instead of the unsaturated trimer. The analogous compounds [{Pt(diphos)(RNC)}2Pt(RNC)2](PF6)2 (diphos = dppen (11) and dtbpe (12)) were also obtained from the reaction of [Pt3-(RNC)8]2+ with diphosphines. Complex 11a (R = 2,6-Me2C6H3) crystallizes in the monoclinic system, space group P2(1)/c, with a = 13.403(3) angstrom, b = 16.126(4) angstrom, c = 21.944(8) angstrom, beta = 98.57(2)degrees, and Z = 2 (R = 0.054 and R(w) = 0.040 for 3064 independent reflections with I > 3 sigma(I)). The Pt-Pt bond length of 2.655(1) angstrom is longer by 0.040 angstrom than that of 13a. A two-electron reduction of 4 at ca. -1.8 V yielded a Hg-Pt mixed-metal cluster, [HgPt6(dppb)2(RNC)8] (17). The length of methylene chain in the diphosphine ligands dramatically influences the structure of the metal-metal bonded platinum clusters. Extended Huckel MO calculations were carried out on the models, [{Pt(PH3)2(HNC)}2Pt]2+ and [{Pt(PH3)2(HNC)}2Pt(HNC)2]2+, for the coordinatively unsaturated and saturated trimers., 1994年04月, ORGANOMETALLICS, 13 (4), 1374 - 1389, web_of_science

    研究論文(学術雑誌)

  • Formation of Nitriles by a Novel Metathesis Reaction of Ruthenium σ-Acetylide Complexes, (η5-indenyl)Ru(η1-C≡CR)(phosphine)2, with Nitric Oxide

    T TANASE; H MOCHIZUKI; R SATO; Y YAMAMOTO

    (eta(5)-In)Ru(eta(1)-C=CPh)(PPh(3))(2) (In = indenyl) treated with nitric oxide (1 atm) in the presence of NaClO4 gave [(eta(5)-In)Ru(CO)(PPh(3))(2)]ClO4.0.5CH(2)Cl(2) and benzonitrile (PhC=N) in good yields, through a novel metathesis reaction between sigma-acetylide and NO. (eta(6)-C(6)Me(6))Ru(eta(1)-C=CPh)(PPh(3))Cl also readily underwent the metathesis reaction with NO to afford benzonitrile., 1994年02月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 466 (1-2), 233 - 236, web_of_science

    研究論文(学術雑誌)

  • SYNTHESIS AND CHARACTERIZATION OF BINUCLEAR PALLADIUM(I) COMPLEXES OF ISOCYANIDES WITH PHENYL-SUBSTITUTED CYCLOPENTADIENYL AND TRIS(PYRAZOL-1-YL)BORATE LIGANDS

    T TANASE; T FUKUSHIMA; T NOMURA; Y YAMAMOTO; K KOBAYASHI

    The reactions of PdCl2(RNC)(2) with potassium pentaphenylcyclopentadienide (K{C(5)Ph(5)}) and potassium tetraphenylcyclopentadienide (K{C(5)HPh(4)}) gave binuclear palladium(I) complexes, Pd-2(eta-C(5)Ph(5))(2)(mu-RNC)(2) (3; R = 2,6-Me(2)C(6)H(3)) and Pd-2(eta-C(5)HPh(4))2 (mu-RNC)(2) (4a, R = 2,6-Me(2)C(6)H(3); 4b, R = 2,4,6-Me(3)C(6)H(2)), in good yields. Complexes 3 and 4 were characterized by elemental analysis, IR, UV-vis, and H-1 and C-13 NMR spectroscopies, and X-ray crystallography. Compound 3 crystallizes in the triclinic system, space group P $$($) over bar 1, with a = 13.391(8) Angstrom, b = 23.793(9) Angstrom, c = 13.681(6) Angstrom, alpha = 90.24(4)degrees, beta = 118.13(4)degrees, gamma = 90.30(4)degrees, and Z = 2 (R = 0.085 and R(w) = 0.088 for 2886 independent reflections with I > 4 sigma(I)), and compound 4b crystallizes in the triclinic system, space group P $$($) over bar 1, with a = 14.907(3) Angstrom, b = 18.794(3) Angstrom, c = 11.769(2) Angstrom, alpha = 101.88(2)degrees, beta = 97.33(2)degrees, gamma = 89.40(2)degrees, and Z = 2 (R = 0.047 and R(w) = 0.038 for 5808 independent reflections with I > 3 sigma(I)). Complexes 3 and 4 consist of two palladium atoms bridged by two isocyanides having the C-N-C linear structure. The Pd2C2 core is folded with the dihedral angles of 121.6 degrees (3) and 137.5 degrees (4b) between the two Pd2C planes. The Pd-Pd bond lengths are 2.632(5) Angstrom (3) and 2.673(1) Angstrom (4b), and the phenyl-substituted cyclopentadienyl groups coordinate to the metal in the distorted eta(5)-fashion. Complex 4 readily reacted with isocyanide to yield the ketenimine compound, Ph(4)C(4)C=C=NR (5). When potassium 1,2,4-triphenylcyclopentadienide (K{C(5)H(2)Ph(3)}) was used, the binuclear palladium(I) complex of isocyanide with bridging eta(3)-C(5)H(2)Ph(3) anions, Pd-2(mu-eta(3)-C(5)H(2)Ph(3))(2)(RNC)(2) (6a, R = 2,6-Me(2)C(6)H(3); 6b, R = 2,4,6-Me(3)C(6)H(2)), was obtained instead of the isocyanide-bridged dimer. Complex 6b crystallizes in the triclinic system, space group P $$($) over bar 1 with a = 11.511(4) Angstrom, b = 12.768(3) Angstrom, c = 10.157(2) Angstrom, alpha = 103.23(2)degrees, beta = 91.71(2)degrees, gamma = 96.83(2)degrees, and Z = 2 (R = 0.034 and R(w) = 0.033 for 5572 independent reflections with I > 3 sigma(I)). In the dimer 6, two eta-C(5)H(2)Ph(3) groups are parallel in an anti arrangement. The Pd-Pd bond length is 2.6309(9) Angstrom. The reaction of Pd2Cl2(RNC)(4) with Na(HB(pz)(3)} (pz = pyrazol-1-yl) produced the dipalladium(I) compound, Pd-2(HB(Pz)3)(mu-RNC2) (8, R = 2,4,6-Me(3)C(6)H(2)), which crystallizes in the monoclinic system, space group P2(1)/n, with a = 11.243(3) Angstrom, b = 15.871(6) Angstrom, c = 12.035(2) Angstrom, beta = 91.99(2)degrees, and Z = 2 (R = 0.062 and R(w) = 0.073 for 1142 independent reflections with I > 3 sigma(I)). Complex 8 consists of two palladium atoms bridged by two isocyanides, and the Pd2C2 core is crystallographically planar. The HB(pz)(3) anion coordinates to the metal in an asymmetrical tridentate manner. The Pd-Pd bond length is considerably elongated to 2.757(4) Angstrom. A linear correlation between the Pd-Pd bond length and the dihedral angle between the two PdC2 planes was observed in the series of Pd-2(mu-RNC)2 dimers. The present work provides an efficient route to a new series of binuclear palladium(I) complexes containing cyclopentadienyl analogues and isocyanides., 1994年01月, INORGANIC CHEMISTRY, 33 (1), 32 - 39, web_of_science

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  • INVERSION OF CONFIGURATION AROUND THE 7-COORDINATED COBALT CENTER INDUCED BY AN INTERACTION BETWEEN SUGARS AND TETRAHEDRAL OXOANIONS

    T TANASE; M NAKAGOSHI; A TERATANI; M KATO; Y YAMAMOTO; S YANO

    Seven-coordinated,cobalt(II) complexes containing N-glycosides from mannose-type aldoses and tris(2-aminoethyl) amine (tren), [Co((aldose) (3)-tren)]X(2). nH(2)O (1a, aldose = D-mannose (D-Man), X = Cl-; 1b, aldose =6-deoxy-L-mannose (L-Rha), X = Cl-; 2a, aldose = D-Man, X = Br; 2b, aldose = L-Rha, X = Br) and [Co((aldose)3-tren)]SO4.nH(2)O (3a, aldose = D-Man; 3b, aldose = L-Rha), were prepared and characterized. The sign of the CD spectra for 1 and 2 containing halide anions is opposite to that of 3 with a SO42- anion, showing the inversion of absolute configuration around the metal center, Delta reversible arrow Lambda induced by an interaction between the sugars and the SO42- anion., 1994年01月, INORGANIC CHEMISTRY, 33 (1), 5 - 6, web_of_science

  • Synthesis and Characterization of Binuclear Palladium(I)Complex of Isocyanides with Bridging η3-Indenyl Ligands, Pd2(μ-η3-indenyl)2(iso-cyanide)2, and its Transformation to Tetranuclear Palladium(I)Cl

    Tomoaki Tanase; Takahito Nomura; Toshihiro Fukushima; Yasuhiro Yamamoto; Kimiko Kobayashi

    The reaction of PdCl2(RNC)2 (RNC = isocyanide) with lithium indenyl (LiIn) gave binuclear palladium(I) complexes, Pd2(mu-eta3-In)2(RNC)2 (3a, R = (t)Bu; 3b, R = 2,6-Me2C6H3; 3c, R = 2,4,6-Me3C6H2; 3d, R = 2,4,6-(t)Bu3C6H2) in moderate yields. Complex 3 was characterized by elemental analysis, IR, UV-vis, and H-1 and C-13 NMR spectroscopies, and X-ray crystallography. Compound 3a crystallizes in the monoclinic system, space group P2(1)/n, with a = 17.254(8) angstrom, b = 9.442(6) angstrom, c = 17.252(6) angstrom, beta = 113.11(3)-degrees, and Z = 4 (R = 0.061 and R(W) = 0.049 for 1930 independent reflections with I > 2.5sigma(I)), and compound 3b crystallizes in the monoclinic system, space group P2(1)/n, with a = 19.235(3) angstrom, b = 9.857(6) angstrom, c = 15.989(9) angstrom, beta = 97.32(3)-degrees, and Z = 4 (R = 0.059 and R(W) = 0.070 for 3250 reflections with I > 2.5sigma(I)). Complex 3 consists of two palladium atoms bridged by two eta3-indenyl groups in a syn arrangement. The Pd-Pd bond lengths are 2.644(3) angstrom (3a) and 2.656(2) angstrom (3b). The two indenyl groups are in a wedge-shaped arrangement, with the dihedral angles of 66.5-degrees (3a) and 47.7-degrees (3b) between the two indenyl planes. The array of Pd2(RNC)2 unit is an A-frame form; the average Pd-Pd-C(RNC) angles are 153.0-degrees (3a) and 163.7-degrees (3b). Complex 3 treated with acetic acid is readily transformed to a tetranuclear palladium(I) cluster of isocyanides, Pd4(mu-OAc)4(mu-RNC)4 (5a, R = (t)Bu; 5b, R = 2,6-Me2C6H3). Cluster 5a crystallizes in the monoclinic system, space group C2/m with a = 18.782(9) angstrom, b = 18.034(9) angstrom, c = 13.420(9) angstrom, beta = 100.07(4)-degrees, and Z = 4 (R = 0.061 and R(W) = 0.064 for 2413 reflections with I > 3sigma(I)). The four palladium atoms lie in a rectangular array with the short Pd-Pd bonds (average 2.650 angstrom) bridged by isocyanides and the long Pd-Pd bonds (average 2.894 angstrom) bridged by acetate ligands. The bridging isocyanides are almost linear (average C-N-C angle = 172-degrees). Extended Huckel MO calculations of the model compounds [Pd4(mu-O2CH)4(mu-HNC)4] (8) and [Pd2-(mu-HNC)2(OH)4]24- (9) were carried out to elucidate the metal-metal bonding systems., 1993年10月, INORGANIC CHEMISTRY, 32 (21), 4578 - 4584, doi;web_of_science

    研究論文(学術雑誌)

  • Studies on Interacation of Isocyanide with Transition Metal Cimplexes XXXVI. Spontaneous Successive Insertion of Isocyanide into Palladium-carbon σ-Bond

    Y YAMAMOTO; T TANASE; T YANAI; T ASANO; K KOBAYASHI

    Reaction of trans-Pd(PPh3)2I(CH3) (1a) with 2,6-xylyl isocyanide in a 1:1 molar ratio led to a spontaneous insertion of isocyanides into a Pd-C bond to give the tris-imino insertion product 2a. The structure was determined by an X-ray analysis. The crystals are triclinic with space group P1 (a = 14.638(9), b = 15.662(7), c = 7.895(3) angstrom, alpha = 85.06(6), beta = 82.84(4), gamma = 102.4(4)-degrees, and Z = 2; R = 0.066 for 2076 independent reflections with F(o) > 5sigma(F(o)). The tris-imino group acts as a bidentate ligand through C- and N-coordinations. The 2-methyl-1-naphthyl complex, trans-Pd(PPh3)Br(2-CH3C10H9) reacted with 2,6-xylyl isocyanide to give a bis-imino complex containing mu2-Br bridging ligands. Using p-nitrophenyl isocyanide,. the reaction produced a mono-imino compound. Reaction of 2a with CuCl2 gave a mixed metal complex, in which the copper(II) atom is coordinated to two neighbouring imino-nitrogens., 1993年09月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 456 (2), 287 - 291, web_of_science

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  • ELECTROCHEMICAL STUDIES OF ORGANOMETALLIC COMPOUNDS .9. ELECTROCHEMICAL PREPARATION AND CHARACTERIZATION OF BINUCLEAR PALLADIUM(I) COMPLEXES CONTAINING AROMATIC ISOCYANIDE AND CHELATING DIPHOSPHINE LIGANDS

    T TANASE; K KAWAHARA; H UKAJI; K KOBAYASHI; H YAMAZAKI; Y YAMAMOTO

    A controlled-potential electrolysis was performed on mononuclear palladium(II) complexes containing aromatic isocyanide (RNC) and diphosphine (diphos) ligands, [Pd(diphos)(RNC)2)](PF6)2 (3) (R = 2,6-dimethylphenyl or 2,4,6-trimethylphenyl, diphos = cis-1,2-bis(diphenylphosphino)ethene (dppen), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane(dppp), or 1,4-bis(diphenylphosphino)butane(dppb)), which were derived from the reaction of PdCl2(COD) with diphos, RNC, and NH4PF6. A controlled-potential electrolysis of the complex 3 at a platinum-plate electrode consumed 1 F mol-1 in acetonitrile at -1.6 V (vs Cp2Fe/CP2Fe+), which gave a binuclear palladium(I) complex, [Pd2(diphoS)2(RNC)2](PF6)2(6). They were characterized by IR, electronic, and H-1 and P-31{H-1} NMR spectroscopies and X-ray crystallographic and EXAFS (extended X-ray absorption fine structure) analysis. The complex 6a (R = 2,6-Me2C6H3, diphos = dppen) crystallizes in the triclinic system, space group P1BAR, with a = 21.346(5) angstrom, b = 14.798(3) angstrom, c = 12.498(3) angstrom, alpha = 71.40(2)-degrees, beta = 103.14(2)-degrees, gamma = 82.92(2)-degrees, and Z = 2 (R = 0.064 and R(w) = 0.075 for 7052 independent reflections with I > 2.5sigma(I)), and the complex 6e (R = 2,4,6-Me3C6H2, diphos = dppp) crystallizes in the monoclinic system, space group P2(1)/a, with a = 25.963(11) angstrom, b = 19.247(4) angstrom, c = 14.963(9) angstrom, beta = 101.49(4)-degrees, and Z = 4 (R = 0.055 and R(w) = 0.058 for 6885 independent reflections with I > 1.5sigma(I)). The complexes 6 consist of two palladium atoms, each of them being coordinated by one isocyanide, one diphosphine, and the neighboring palladium atom in a square planar array. The diphosphines acted as chelating ligands. The lengths of the Pd-Pd bond fall within the range 2.59-2.62 angstrom, indicating that the Pd-Pd bond was hardly affected by the length of carbon chains of chelating diphosphines., 1993年08月, INORGANIC CHEMISTRY, 32 (17), 3682 - 3688, web_of_science

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  • BIS(2-BROMOETHYL)SELENIUM DIBROMIDE AS THE SELENIUM-INTRODUCING REAGENT - ONE-POT PREPARATION OF 2,5-BIS(ALKOXYMETHYL)TETRAHYDROSELENOPHENES BY THE CYCLIZATION OF 1,5-HEXADIENE

    Y TAKANOHASHI; N TABATA; T TANASE; S AKABORI

    The reaction of bis(2-bromoethyl)selenium dibromide (1a) with 1,5-hexadiene (2) in methanol or ethanol affords 2,5-bis(alkoxymethyl)tetrahydroselenophene-1,1-dibromides (R = CH3 (3b), R = C2H5 (3c)) via 2,5-bis(bromomethyl)tetrahydroselenophene-1,1-dibromide (3a). The reaction of 1a with 2 in 1-propanol, 2-methyl-1-propanol or 1-butanol in the presence of sodium carbonate gave 2,5-bis(alkoXyMethyl)tetrahydroselenophene (R = C3H7 (4a), R = (CH3)2CHCH2 (4b) and R = C4H9 (4c)) via 3a. The ratios of the trans and cis isomers of 3a-3c are 3:2. In addition, the structure of trans-2,5-bis(methoxymethyl)tetrahydroselenophene-1,1-dibromide (trans-3b) was determined by X-ray crystallography., 1993年05月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 450 (1-2), 103 - 108, web_of_science

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  • SELENIUM TRANSFER REAGENT - ONE-STEP ALKOXYSELENATION OF CYCLOHEXENE WITH BIS(2-BROMOETHYL)SELENIUM DIBROMIDE

    Y TAKANOHASHI; N TABATA; T TANASE; S AKABORI

    The reaction of bis(2-bromoethyl)selenium dibromide 1 with cyclohexene 2 in alcohol under reduced pressure proceeds smoothly to give bis(2-alkoxycyclohexyl)selenium dibromide (R = Me 4, R = Et 5, R = Pr(i) 6) via 2-bromocyclohexyl-2'-bromoethylselenium dibromide 3 as an intermediate together with ethene. The diastereoisomers 4a and 5a (1R,2R,1'S,2'S) and 4b and 5b (1R,2R,1'R,2'R or 1S,2S,1'S,2'S) were separated from 4 and/or 5. These isomers 4a/5a and 4b/5b were isolated as a meso and a racemic mixture, respectively. Although the addition product 6a (1R,2R,1'S,2'S) was only isolated from 6 in the meso form, the corresponding diastereoisomer 6b (1R,2R,1'R,2'R or 1S,2S,1'S,2'S) was not detected. These results indicated that the Se and Br atoms in the cyclohexane ring of 3, and the Se and alkoxy groups in the cyclohexane rings of 4-6 were in the diequatorial position., 1993年04月, JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, (7), 813 - 817, web_of_science

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  • NEW CHIRAL LANTHANIDE COMPLEXES WITH OPTICALLY PURE ETHANEDIYLBIS(T-BUTYLPHENYLPHOSPHINE OXIDE)

    Y KOIDE; A SAKAMOTO; T IMAMOTO; T TANASE; Y YAMAMOTO

    New chiral lanthanide(III) complexes have been prepared by the reaction of lanthanide(III) halides with optically pure (R,R)-1,2-ethanediylbis(t-butylphenylphosphine oxide). The cerium(III) chloride complex is structurally characterized by X-ray crystallography. Tetravalent cerium chloride and nitrate complexes with the same ligand are also prepared and characterized., 1993年02月, JOURNAL OF ALLOYS AND COMPOUNDS, 192 (1-2), 211 - 216, web_of_science

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  • Synthesis and Characterization of Nickel(II) Complexes and 1,3-Diaminopropane

    T. Tanase; R. Nouchi; Y. Oka; M. Kato; N. Nakamura; T. Yamamura; Y. Yamamoto; S. Yano

    The reaction of [Ni(tn)3]2+ ions (tn = 1,3-diaminopropane) with disaccharides having a glucose reducing terminal, i.e. maltose, lactose, cellobiose, and melibiose, in the presence of a catalytic amount of ammonium chloride gave blue, Paramagnetic bis(N-D-aldosylpropane-1,3-diamine)nickel(II) complexes. The complexes were characterized by elemental analysis, magnetic susceptibilities, electronic absorption and circular dichroism spectroscopies, X-ray absorption and crystallographic analyses. The complex bis[N-(4-O-alpha-D-glucopyranosylglucosyl)propane-1,3-diamine]nickel(II) bromide dihydrate crystallizes in the hexagonal space group P6(4)22, with a = 22.125(8), c = 21.464(9) angstrom, and Z = 6. The structure was solved by Patterson methods and refined by full-matrix least-squares techniques to R = 0.080 and R' = 0.094. The complex cation has C2 symmetry and the central nickel atom is octahedrally coordinated by two tridentate glycosylamine ligands formed from maltose and tn. Each ligand is bonded through the oxygen atom of the hydroxyl group at C2 of maltose and through the two nitrogen atoms of the diamine in a meridional mode. The co-ordination behaviour of the glucose unit in the octahedral nickel(II) complexes has been established. In the crystal packing, the complex cation exists in a novel dimeric form supported by intermolecular hydrogen bonds, which might provide some fundamental information concerning sugar-sugar interactions in biological systems., 1993年, J. Chem. Soc., DALTON TRANS., 1993 (17), 2645 - 2652, web_of_science

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  • Synthesis and Characterization of Copper(II) Complexes Containing N-Glycoside Ligands and Their Use in the Catalytic Epoxidation of Olefins

    Tomoaki Tanase; Keisuke Mano; Yasuhiro Yamamoto

    The reaction of copper(II) salts with aldoses and ethylenediamine (en) gave new types of copper(II) complexes containing N-glycoside ligands, Cu(N,N′-(aldose)2-en)X2 (3) (N,N′-(aldose)2-en = l,2-bis(aldosylamino)ethane aldose = d-glucose, d-mannose, d-xylose, d-lyxose X = Cl−, Br−). The structure was determined by electronic absorption and circular dichroism spectroscopies, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS), in which Cu(hen(OH))X2 (1) and Cu(hen(OH)2)X2 (2) were used as reference compounds (X = Cl, Br hen(OH) = l-amino-2-((2-hydroxyethyl)amino)ethane hen(OH)2 = 1,2-bis-((2-hydroxyethyl)amino)ethane). The complexes 3 have a mononuclear [CuIIN2OX] square planar structure. The N,N′-(aldose)2-en moiety acts as a tridentate ligand through the two amino groups and the hydroxy group at the C-2 position of the aldoses. When N,N′-dimethylethylenediamine (N,N′-Me2en) and N,N-dimethylethylenediamine (N,N-Me2en) were used, similar copper(II) complexes containing a tridentate N-glycoside ligand, Cu(N-(aldose)-N,N′-Me2en)X2 (4) and Cu(N′-(aldose)-N,N-Me2en)Cl2 (5) (aldose = d-glucose, d-mannose X = Cl−, Br−), were obtained. The sugar complexes 3–5 interestingly catalyzed the epoxidation of unfunctionalized olefins ((E)-stilbene, (Z)-stilbene, (E)-β-methylstyrene) with tert-butyl hydroperoxide, but the enantioselectivities were low. In contrast, (E)-cinnamyl acetate having a polar functional part was converted into its epoxide with an enantiomeric excess of 16%. © 1993, American Chemical Society. All rights reserved., 1993年, Inorganic Chemistry, 32 (19), 3995 - 4003, doi

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  • UPTAKE OF A HG OR HG2 UNIT INTO THE CENTER OF CAGE-TYPE PLATINUM CLUSTERS SUPPORTED BY DIPHOSPHINES HAVING LONG METHYLENE CARBON CHAINS - X-RAY STRUCTURE OF [HG2PT6(DPPHEX)3(RNC)6].2C6H6 (DPPHEX = 1,6-BIS(DIPHENYLPHOSPHINO)HEXANE, R = 2,6-DIMETHYLPHENYL)

    T TANASE; T HORIUCHI; Y YAMAMOTO; K KOBAYASHI

    When Pt(COD)Cl2 was treated with sodium amalgam in the presence of aromatic isocyanide (RNC, R = 2,6-Me2C6H3 (Xyl) or 2,4,6-Me3C6H2 (Mes)) and diphosphine with long methylene chain (diphos = Ph2P(CH2)nPPh2, n = 5 (dpppn) or 6 (dpphex)), two kinds of Hg-Pt mixed metal clusters, [Hg2Pt6(diphos)2(RNC)8] (2) and [Hg2Pt6(diphos)3(RNC)6] (3), were obtained. The structure of 3b (R = Xyl, diphos = dpphex) was determined by an X-Tay analysis to be a cage-type cluster where a Hg2 unit was incorporated into a trigonal-anti-prismatic platinum core, two Pt3 triangles being supported by three dpphex ligands (close-type). The cluster 2 was assumed to have an incomplete cage-type structure (open-type), and was converted to close-type 3 by treatment with an equivalent diphosphine ligand. When dppb (n = 4) was used, an open-type mixed metal cluster in which one mercury atom was captured, [HgPt6(dppb)2(RNC)8] (4), was obtained as the sole product., 1992年11月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 440 (1-2), 1 - 5, web_of_science

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  • SYNTHESIS OF MIXED-METAL SULFIDO CLUSTERS WITH A CUBOIDAL MO3PDS4 CORE WHICH COORDINATE ALKENE TO THE UNIQUE PALLADIUM SITE SURROUNDED BY SULFIDO LIGANDS

    T MURATA; H GAO; Y MIZOBE; F NAKANO; S MOTOMURA; T TANASE; S YANO; M HIDAI

    1992年10月, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 114 (21), 8287 - 8288, web_of_science

  • MESOGENICITY OF 4-ALKANOYL-4'-ALKYLOXYBIPHENYL DERIVATIVES

    T TANASE; S YANO

    Phase transitions of 4-alkanoyl-4'-alkyloxybiphenyl were studied by differential scanning calorimetry and optical microscopy. 4-Acetyl-4'-alkyloxybiphenyl homologues (number of carbon atoms, of n, 4'-alkyloxy group is 4-10) showed S(E) phases with good thermal stability, while 4-propionyl-4'-alkyloxybiphenyl homologues (n = 4-10) and 4-pentanoyl-4'-decyloxybiphenyl showed S(A) phases with good thermal stability. Moreover changes in the thermal stability by substitution of bulky Br, Cl or CH3 substituents into the alkanoyl groups were studied for the previously mentioned three homologues. The substitution at the alpha-position of the alkanoyl group was found to strikingly lower the thermal stability., 1992年08月, LIQUID CRYSTALS, 12 (2), 297 - 303, web_of_science

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  • C-2 EPIMERIZATION OF ALDOSES PROMOTED BY COBALT(II) N-ALKYLATED DIAMINE COMPLEXES, INVOLVING A STEREOSPECIFIC REARRANGEMENT OF THE CARBON SKELETON

    T TANASE; T TAKEI; M HIDAI; S YANO

    1992年08月, JOURNAL OF CHEMICAL RESEARCH-S, (8), 252 - 253, web_of_science

    研究論文(学術雑誌)

  • FORMATION OF HETEROBICYCLIC COMPOUNDS THROUGH SUCCESSIVE INSERTION OF ISOCYANIDES INTO A PALLADIUM HYDRIDE BOND

    T TANASE; T OHIZUMI; K KOBAYASHI; Y YAMAMOTO

    Reaction of PdCl2(PPh3)2 1 with an excess of H2SiMePh and 2,6-xylyl isocyanide gives Pd{C(= NR)C(= NR)C(= NR)C(= NR)CH(= NR)}(C = NR)Cl.1/2C6H6 (3, R = 2,6-xylyl) and heterobicyclic compound, 2,6-(2',6'-xylyl)2-3,7-(N-2',6'-xylylimino)2-4,8-(N-2',6'-xylylamino)2-2,6-diaza-bicyclo[3.3.0]octa-4,8-diene 4; the structures of which have been determined by X-ray analysis., 1992年05月, JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, (9), 707 - 708, web_of_science

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  • A NOVEL DINUCLEAR TETRACARBONYL COMPLEX CONTAINING A BRIDGING ALKYLDIAZENIDO LIGAND [WCL(CO)2(PME2PH)2(N=NCME2CME2N=N)WCL(CO)2(PME2PH)2] FORMED VIA A CATIONIC CARBONYLDIAZOALKANE COMPLEX [WCL(CO)(NN=CME2)(PME2PH)3][ZNCL3(THF)]

    T AOSHIMA; T TANASE; Y MIZOBE; Y YAMAMOTO; M HIDAI

    Treatment of a diazoalkane complex mer-[WCl2(NN = CMe2)(PMe2Ph)3] with CO in the presence of ZnCl2(dioxane) affords a cationic carbonyldiazoalkane complex [WCl(CO)(NN = CMe2)(PMe2Ph)3] [ZnCl3(thf)] (thf = tetrahydrofuran), in which the carbon-carbon coupling of the diazoalkane ligand occurs by reduction with Mg under CO to give a dinuclear tetracarbonyldiazenido complex [WCl(CO)2(PMe2Ph)2(N = NCMe2CMe2N = N)WCl(CO)2(PMe2Ph)2]., 1992年04月, JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, (7), 586 - 588, web_of_science

    研究論文(学術雑誌)

  • SPONTANEOUS FIXATION OF CARBON-DIOXIDE IN AIR BY A NICKEL DIAMINE COMPLEX - SYNTHESIS AND CHARACTERIZATION OF A TRINUCLEAR NICKEL(II) COMPLEX WITH A NOVEL HYDROGEN-BONDING SYSTEM AROUND A CARBONATE LIGAND

    T TANASE; S NITTA; S YOSHIKAWA; K KOBAYASHI; T SAKURAI; S YANO

    The nickel(II) complex of N,N-dimethylethylenediamine (N,N-Me2en), [Ni(N,N-Me2en)3](ClO4)2 (1), in aqueous ethanol spontaneously adsorbed and fixed CO2 in air to give a trinuclear nickel(II) complex, [Ni3(N,N-Me2en)6(CO3)(H2O)4](ClO4)4 (2). The complex 2 crytallizes in the hexagonal system, space group P6(3), with a = 25.824 (7) angstrom, c = 14.506 (3) angstrom, and Z = 6. The structure was solved by direct methods and refined by least-squares techniques to a final R value of 0.065 for 2940 independent reflections with F(o) > 3-sigma(F(o)). The absolute configuration was determined by the Bijvoet method. The complex cation is trinuclear, which is made up of three octahedral nickel(II) complexes, LAMBDA-cis-(O,O)-[Ni(N,N-Me2en)2(CO3)] and LAMBDA- and DELTA-cis-(O,O)-[Ni(N,N-Me2en)(H2O)2]2+, joined by a novel hydrogen bonding network around the coordinating carbonate ligand. This planar hydrogen bonding system might stabilize the bidentate carbonate, resulting in the spontaneous fixation of CO2 in air. When analogous diamines (N,N'-dimethylethylenediamine, N,N-diethylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine) were used instead of N,N-Me2en, no fixation of CO2 was observed. The N-substituent of diamines is an important factors in determining the occurrence of CO2 uptake., 1992年03月, INORGANIC CHEMISTRY, 31 (6), 1058 - 1062, web_of_science

    研究論文(学術雑誌)

  • Chemistry of Polynuclear Palladium and Platinum Complexes Involving Metal-Metal Bonds ; Searching for Model Compounds between Hetero-geneous and Homogeneous Catalysts

    Tomoaki Tanase

    1992年, Chemistry and Chemical Industry(Japan), 45, 244-248

  • Syntheses and Characterization of Complexes Derived from α-Amino-malonate and trans-[CoCl2(2,3,2-tet)]+

    T KOJIMA; T USUI; A SHIMADA; M YASHIRO; T TANASE; R YOSHIOKA; R KURODA; S YANO; M HIDAI; M KATO; K KOBAYASHI; T SAKURAI; S YOSHIKAWA

    The reaction of alpha-aminomalonate (AM2-) with trans-[CoCl2(2,3,2-tet)]ClO4 (2,3,2-tet = 1,9-diamino-3,7-diazanonane) (1) in MeOH in the presence of Et3N under aerobic conditions gave an AM2- complex (2), unusually stabilized alpha-diamine complexes (3, 4), and a carbinolamine complex (5). The X-ray crystallographic study was undertaken on [Co(AM)(2,3,2-tet)]ClO4.H2O (2) and the alpha-diamine complexes [Co(N-(2-aminoethyl)-N-(6-amino-4-azahexyl)-alpha,alpha-diaminomalonato)]ClO4 (3) and [Co(N-(9-amino-3,7-diazanonyl)-alpha,alpha-diaminomalonato)]ClO4.H2O (4), and the following data were obtained. For compound 2: C10-H23N5O4CoClO4.H2O, monoclinic, space group Cc, a = 13.856 (2) angstrom, b = 11.466 (2) angstrom, c = 11.898 (3) angstrom, beta = 107.32 (1)-degrees, Z = 4, R = 0.057, R(w) = 0.066. For compound 3: C10H21N5O4CoClO4, monoclinic, space group P2(1)/c, a = 7.399 (5) angstrom, b = 23.199 (5) angstrom, c = 9.452 (4) angstrom, beta = 92.02 (5)-degrees, Z = 4, R = 0.050, R(w) = 0.052. For compound 4: C10H21N5O4CoClO4.H2O, space group P2(1)/c, a = 7.360 (2) angstrom, b = 13.571 (3) angstrom, c = 17.370 (6) angstrom, beta = 91.02 (2)-degrees, Z = 4, R = 0.067, R(w) = 0.070. The C-N bond formation between AM2- and the amine ligand was promoted by dioxygen, Co(III) ion, heat, and MeOH and was enhanced photoinductively. The carbinolamine complex 5 was also obtained from the reaction of ketomalonate anion (KM2-) with 1 in MeOH in the presence of NEt3. X-ray crystallographic study on the carbinolamine complex, [Co(N-(9-amino-3,7-diazanonyl)-alpha-amino-alpha-hydroxylmalonato)]ClO4.H2O (5) was also performed: C10H20N4O5CoClO4.H2O, orthorhombic, space group P2(1)2(1)2(1), a = 7.291 (1) angstrom, b = 13.408 (2) angstrom, c = 17.143 (3) angstrom, Z = 4, R = 0.061, R(w) = 0.066. The results of X-ray crystallography and pK(a) measurements indicated that the uncoordinated NH2 or OH groups of 3, 4, and 5 had some properties which were similar to those of an anilinic amino group or a phenolic hydroxy group in spite of being bound to the sp3 carbon atoms., 1991年11月, INORGANIC CHEMISTRY, 30 (24), 4535 - 4541, web_of_science

    研究論文(学術雑誌)

  • C-2 EPIMERIZATION OF DISACCHARIDES BY CALCIUM(II) - MONOAMINE SYSTEMS - A DIRECT SYNTHESIS OF (1-]4)-LINKED DISACCHARIDES HAVING A D-MANNOSE UNIT AS A REDUCING TERMINAL

    T TAKEI; T TANASE; S YANO; M HIDAI

    (1 --> 4)- and (1 --> 6)-linked disaccharides were epimerized at C-2 of the reducing terminal under mild conditions by calcium(II) - N-alkylated monoamine systems. Naturally rare (1 --> 4)-linked heterodisaccharides having a D-mannose unit as a reducing terminal can be prepared in one step from disaccharides having a D-glucose unit which are abundunt in nature., 1991年09月, CHEMISTRY LETTERS, (9), 1629 - 1632, web_of_science

    研究論文(学術雑誌)

  • PREPARATION AND PROPERTIES OF MOLYBDENUM AND TUNGSTEN DINITROGEN COMPLEXES .32. A SERIES OF NOVEL CARBONYL-COMPLEXES OF TUNGSTEN DERIVED FROM THE DINITROGEN COMPLEX TRANS-[W(N2)2(PH2PCH2CH2PPH2)2]

    T ISHIDA; Y MIZOBE; T TANASE; M HIDAI

    Treatment of trans-[W(N2)2(dppe)2] (dppe=Ph2PCH2CH2PPh2) with N,N-dimethylformamide (DMF) in benzene under reflux afforded trans-[W(CO)(DMF)(dppe)2], together with a hydridocarbamoyl complex [WH(eta-2-CONMe2)(dppe)2] as the intermediate stage of this decarbonylation reaction. The detailed structure of the latter complex was determined by X-ray crystallography. Reaction of trans-[W(CO)(DMF)(dppe)2] with N2 afforded trans-[W(CO)(N2)(dppe)2], whose solution in benzene was further converted into a coordinatively unsaturated complex [W(CO)(dppe)2] under reflux in an Ar atmosphere. Subsequent treatment of [W(CO)(dppe)2] with H2 gas gave a dihydrido complex [WH2(CO)(dppe)2]., 1991年06月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 409 (3), 355 - 365, web_of_science

    研究論文(学術雑誌)

  • Synthesis and Characterization of Binuclear Palladium Complexes of Isocyanides with Novel Bridging η3-Indenyl Ligands : Crystal Structure of [Pd2(μ-η3-indenyl)2(RNC)2]

    T TANASE; T NOMURA; Y YAMAMOTO; K KOBAYASHI

    The reaction of PdCl2(RNC)2 (RNC = isocyanide) with indenyl lithium (InLi) gave a binuclear palladium complex, [Pd2(mu-eta-3-In)2(RNC)2], in which the Pd2(RNC)2 unit is sandwiched between two-mu-eta-3-indenyl groups in a syn arrangement., 1991年06月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 410 (2), C25 - C28, web_of_science

    研究論文(学術雑誌)

  • Cobalt-catalyzed Preparation of Diiminofuran Derivatives through Double Insertion of Isocyanide into a Metal-Carbon σ-Bonds

    K SUGANO; T TANASE; K KOBAYASHI; Y YAMAMOTO

    The reaction of 2-bromoacetophenone with XylNC (Xyl = 2,6-xylyl) in the presence of Et3N and cobalt complex such as Co2(XylNC)8, CoBr2(XylNC)4, [Co(XylNC)5] (PF6) or Co(acac)3, gave 2,3-bis-N-(2',6'-xylyl)imino-5-phenyl-2,3-dihydrofuran. The structure was confirmed by an X-ray crystallographic analysis., 1991年06月, CHEMISTRY LETTERS, (6), 921 - 924, web_of_science

    研究論文(学術雑誌)

  • PREPARATION AND PROPERTIES OF MOLYBDENUM AND TUNGSTEN DINITROGEN COMPLEXES .30. SYNTHESIS OF ZERO-VALENT MOLYBDENUM COMPLEXES WITH THE DMF LIGAND - THE CRYSTAL-STRUCTURE OF TRANS-[MO(CO)(DMF)(PH2PCH2CH2PPH2)2]

    Y MIZOBE; T ISHIDA; Y EGAWA; K OCHI; T TANASE; M HIDAI

    1991年, JOURNAL OF COORDINATION CHEMISTRY, 23 (1-4), 57 - 66, web_of_science

    研究論文(学術雑誌)

  • Preparation and Properties of Molybdenum and Tungsten Dinitrogen Complexes 30. Synthesis of Zero-valent Molybdenum Complexes with DMF Ligand and the X-ray structure of trans-[Mo(CO)(DMF)(dppe)2]

    TANASE Tomoaki; Y. Mizobe; T. Ishida; Y. Egawa; K. Ochi; T. Tanase; M. Hidai

    1991年, J. Coord. Chem., 23, 57-66

  • Preparation and Properties of Molybdenum and Tungsten Dinitrogen Complexes XXXII. A Series of Novel Carbonyl Complexes Derived from Dinitrogen Complex trans-[W(N2)2(dppe)2]

    TANASE Tomoaki; T. Ishida; Y. Mizobe; T. Tanase; M. Hidai

    1991年, J. Organomet. Chem., 409, 355-365

  • A TRI-PLATINUM COMPLEX CONTAINING A COORDINATIVELY NAKED PLATINUM ATOM

    T TANASE; Y KUDO; M OHNO; K KOBAYASHI; Y YAMAMOTO

    1990年04月, NATURE, 344 (6266), 526 - 528, web_of_science

    研究論文(学術雑誌)

  • ELECTROCHEMICAL STUDIES OF ORGANOMETALLIC COMPOUNDS .5. ELECTROCHEMICAL REACTIONS OF RUTHENIUM(II) ISOCYANIDE COMPLEXES

    Y YAMAMOTO; T TANASE; T DATE; Y KOIDE; K KOBAYASHI

    1990年04月, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 386 (3), 365 - 374, web_of_science

    研究論文(学術雑誌)

  • Synthesis and Characterization of Cobalt(III) Complexes Containing α-Diamine and Carbinolamine Derived from α-Aminomalonate and Ethylenediamine

    T KOJIMA; T USUI; T TANASE; M YASHIRO; S YOSHIKAWA; R KURODA; S YANO; M HIDAI

    1990年02月, INORGANIC CHEMISTRY, 29 (3), 446 - 450, web_of_science

    研究論文(学術雑誌)

  • NOVEL C-2 EPIMERIZATION OF ALDOSES PROMOTED BY NICKEL(II) DIAMINE COMPLEXES, INVOLVING A STEREOSPECIFIC PINACOL-TYPE 1,2-CARBON SHIFT

    T TANASE; F SHIMIZU; M KUSE; S YANO; M HIDAI; S YOSHIKAWA

    1988年11月, INORGANIC CHEMISTRY, 27 (23), 4085 - 4094, web_of_science

    研究論文(学術雑誌)

  • AN EXAFS STUDY OF BINUCLEAR RUTHENIUM(III) COMPLEXES WITH 2 AND 3 BRIDGING THIOLATE LIGANDS

    T TANASE; K IMAGAWA; S DEV; Y MIZOBE; S YANO; M HIDAI

    1988年06月, NEW JOURNAL OF CHEMISTRY, 12 (6-7), 697 - 698, web_of_science

  • PREPARATION AND PROPERTIES OF MOLYBDENUM AND TUNGSTEN DINITROGEN COMPLEXES .24. DECARBONYLATION REACTION OF DIMETHYLFORMAMIDE (DMF) WITH TRANS-[W(N2)2(PH2PCH2CH2PPH2)2] - PREPARATION AND CHARACTERIZATION OF [WH(ETA-2-CONME2)(PH2PCH2CH2PPH2)2] AND [W(CO)(DMF)(PH2PCH2CH2PPH2)2]

    T ISHIDA; Y MIZOBE; T TANASE; M HIDAI

    1988年03月, CHEMISTRY LETTERS, (3), 441 - 444, web_of_science

    研究論文(学術雑誌)

  • C-2 EPIMERIZATION OF DISACCHARIDES BY NICKEL(II)-DIAMINE COMPLEX - A NEW SYNTHESIS OF (1-]6)-LINKED DISACCHARIDES HAVING MANNOSE AS A REDUCING UNIT

    T TANASE; K ISHIDA; T WATANABE; M KOMIYAMA; K KOUMOTO; S YANO; M HIDAI; S YOSHIKAWA

    1988年02月, CHEMISTRY LETTERS, (2), 327 - 330, web_of_science

    研究論文(学術雑誌)

  • Tris(1R, 2R-cyclohexanediamine)nickel(II)Bromide Trihydrate

    TANASE Tomoaki; K. Ishida; T. Tanase; T. Takahashi; Y. sato; S. Yano; K. Kobayashi; T. Sakurai

    1988年01月, ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 44, 83 - 85, web_of_science

    研究論文(学術雑誌)

  • STRUCTURE OF 5-NITRO-2-([(S)-1-PHENYLETHYL]AMINO)PYRIDINE

    T KONDO; N OGASAWARA; R ITO; K ISHIDA; T TANASE; T MURATA; M HIDAI

    1988年01月, ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 44, 102 - 104, web_of_science

    研究論文(学術雑誌)

  • An EXAFS Study of Binuclear Ruthenium(III)Complexes with Two and Three Bridging Thiolate Ligands

    T. Tanase; K. Imagawa; S. Dev; Y. Mizobe; S. Yano; M. Hidai

    1988年, New J. Chem., 12, 697-698

  • Decarbonylation Reaction of DMF with trans-[W(N2)2(dppe)2]. Preparation and Characterization of [WH(η2-CONMe)(dppe)2]and [W(CO)(DMF)(dppe)2]

    TANASE Tomoaki; T. Ishida; Y. Mizobe; T. Tanase; M. Hidai

    1988年, Chem. Lett., 441-444

  • REACTION OF [NI(H2O)2(N,N'-ME2-EN)2]2+ WITH CARBOHYDRATES - SYNTHESIS AND CHARACTERIZATION OF A NOVEL MU-MANNOFURANOSIDE BINUCLEAR NICKEL(II) COMPLEX CONTAINING N-GLYCOSIDES

    T TANASE; K KURIHARA; S YANO; K KOBAYASHI; T SAKURAI; S YOSHIKAWA; M HIDAI

    1987年09月, INORGANIC CHEMISTRY, 26 (19), 3134 - 3139, web_of_science

    研究論文(学術雑誌)

  • C-2 EPIMERIZATION OF ALDOSES PROMOTED BY COMBINATIONS OF METALS AND DIAMINES INVOLVING A NOVEL REARRANGEMENT OF THE CARBON SKELETON

    T TANASE; F SHIMIZU; M KUSE; S YANO; S YOSHIKAWA; M HIDAI

    1987年05月, JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, (9), 659 - 661, web_of_science

    研究論文(学術雑誌)

  • MOLECULAR RECOGNITION OF MANNOSE-TYPE ALDOSES BY NICKEL(II) DIAMINE COMPLEXES - AN EXAFS STUDY OF NI(II) COMPLEXES CONTAINING CARBOHYDRATES

    T TANASE; F SHIMIZU; S YANO; M HIDAI; S YOSHIKAWA; K ASAKURA

    1987年03月, NIPPON KAGAKU KAISHI, 3 (3), 322 - 327, web_of_science

    研究論文(学術雑誌)

  • A NOVEL SUGAR-SUGAR INTERACTION IN A TRANSITION-METAL COMPLEX - X-RAY CRYSTAL-STRUCTURE OF N,N-DI(N-D-MANNOSYL-2-AMINOETHYL)-ETHYLENEDIAMINE NICKEL(II) DICHLORIDE METHANOL, [NI(N,N'-(D-MAN)2-TREN)]CL2.CH3OH

    S YANO; T TAKAHASHI; Y SATO; K ISHIDA; T TANASE; M HIDAI; K KOBAYASHI; T SAKURAI

    1987年, CHEMISTRY LETTERS, (11), 2153 - 2156, web_of_science

    研究論文(学術雑誌)

  • C-2 EPIMERIZATION OF ALDOSES PROMOTED BY COMBINATION OF MONOAMINES AND ALKALINE-EARTH OR RARE-EARTH METAL-IONS, INVOLVING A REARRANGEMENT OF THE CARBON SKELETON

    T TANASE; T MURATA; S YANO; M HIDAI; S YOSHIKAWA

    1987年, CHEMISTRY LETTERS, (7), 1409 - 1412, web_of_science

    研究論文(学術雑誌)

  • NOVEL C-2 EPIMERIZATION OF ALDOSES AND STEREOSELECTIVE UPTAKE OF ONE OF THE EPIMERIC ALDOSES BY NICKEL(II) COMPLEXES

    T TANASE; F SHIMIZU; S YANO; S YOSHIKAWA

    1986年07月, JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, (13), 1001 - 1003, web_of_science

    研究論文(学術雑誌)

  • Reaction of Metal Complexes with Carbohydrates : Synthesis and Characterization of an Unprecedented μ-Mannofuranoside Binuclear Nickel(II)Complex Containing N-Glycosides

    T TANASE; K KURIHARA; S YANO; K KOBAYASHI; T SAKURAI; S YOSHIKAWA

    1985年, JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, (22), 1562 - 1563, web_of_science

    研究論文(学術雑誌)

  • Tetranuclear Rh4 chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) capturing H2 to afford Rh4H3 hydride complexes

    Tomoaki Tanase; Yuka Morita; Kazuki Sato; Risa Aoki; Akiko Yoshii; Kanako Nakamae; Yasuyuki Ura; Takayuki Nakajima

    2021年03月10日, Journal of Organometallic Chemistry, 939, 121771-1 - 121771-11, 国際誌, doi;scopus;scopus_citedby

    研究論文(学術雑誌)

  • Chiral Octapalladium Chains Supported by Enantiopure P-Stereogenic Linear Tetraphosphines, (R,R)- and (S,S)-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2

    Tomoaki Tanase; Kanako Nakamae; Suzui Hayashi; Ayumi Okue; Risa Otaki; Tomoko Nishida; Yasuyuki Ura; Yasutaka Kitagawa; Takayuki Nakajima

    2021年03月01日, Inorganic Chemistry, 60 (5), 3259 - 3273, 国際誌, doi;pubmed;url;scopus;scopus_citedby

    研究論文(学術雑誌)

MISC

  • 特集 錯体研究におけるポイント解説~金属クラスター編~「1次元に拡張した分子性金属鎖を目指して」

    錯体化学会, 2020年11月30日, Bull. Jpn. Soc. Coord. Chem., 2020, 76, 58-60

  • トピックス『直鎖状多座ホスフィンにより構造規制された遷移金属クラスター ―分子性金属鎖の化学を中心に―』

    棚瀬知明

    2019年04月01日, Organometallic News, 2019 (1), 14 - 19, 国内誌

    記事・総説・解説・論説等(学術雑誌)

  • 分子性金属鎖の化学―分子デバイスのための金属ワイヤーを目指して

    中島隆行; 棚瀬知明

    2017年04月01日, 化学, 72 (4), 66 - 67, 国内誌

    記事・総説・解説・論説等(商業誌、新聞、ウェブメディア)

  • ナノテクノロジーExpress -ナノテクノロジープラットフォームから飛び立つ成果- 第33回 カーボンナノチューブを搭載したフレキシブルπ型熱電発電シート

    棚瀬知明; 野々口斐之

    2014年12月, NanotechJapan Bulletin, 7

    記事・総説・解説・論説等(商業誌、新聞、ウェブメディア)

  • 1次元に拡張した分子性金属鎖を目指して

    棚瀬知明; 中前佳那子; 中島隆行

    2020年11月30日, Bulletin of Japan Society of Coordination Chemistry, 76, 48 - 50, 国内誌

書籍等出版物

  • 錯体化合物事典

    錯体化学会

    朝倉書店, 2019年09月, 54, 944p, 5, cinii_books (ISBN: 9784254141054)

  • 「ハウスクロフト 無機化学 (上)」

    棚瀬知明; 巽; 西原; 穐田; 酒井監訳; 棚瀬他 (, 範囲: 分担)

    東京化学同人(東京), 2012年03月, 2,3,6章分担翻訳

  • 「ハウスクロフト 無機化学 (下)」

    棚瀬知明; 巽; 西原; 穐田; 酒井監訳; 棚瀬他 (, 範囲: 分担)

    東京化学同人(東京), 2012年03月, 28章分担翻訳

  • 実験化学講座22 金属錯体・遷移金属クラスター(第5版)

    棚瀬知明; 日本化学会編 (, 範囲: 分担)

    丸善株式会社, 2004年

  • 無機・分析化学演習 : 大学院入試問題を中心に

    竹田, 満洲雄; 高橋, 正; 棚瀬, 知明; 北澤, 孝史

    東京化学同人, 1998年04月01日, iv, 383p, 65-170p, cinii_books (ISBN: 4807904744)

  • 生物無機化学

    棚瀬知明; 棚瀬, 松本; 坪村, 酒井 (, 範囲: 分担)

    東京化学同人, 1997年

  • 有機金属化学辞典

    棚瀬知明; 有機金属化学事典編集委員会監訳; 訳; 分担執筆 (, 範囲: 分担)

    朝倉書店, 1996年

  • 錯体化学ー有機・無機複合体の分子科学

    棚瀬知明; 石井洋一編著; 猪俣智彦; 梶原孝志; 北河康隆共著 (, 範囲: 1-3章,10-1~2章,11-4章)

    三共出版, 2021年03月15日, 496, 150 (ISBN: 9784782708002)

講演・口頭発表等

  • Self-Alignment of Low-Valent Palladium Chains with meso/rac-tetraphosphine, Self-Chiral Recognition of Pd4 Units

    T. Tanase

    4th Japan-Canada Joint Symposium on Coordination Chemistry, (November 26-30, 2017, Fukuoka-Miyazaki, Japan)

  • Self-Alignment of Low-Valent Palladium Chains with meso/rac-tetraphosphine, Self-Chiral Recognition of Pd4 Units

    T. Tanase

    4th Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry, (2017,12,10-13, Hong Kong, China)

  • 直鎖状多座ホスフィンにより構造規制された遷移金属クラスター ―分子性金属鎖の化学を中心に―

    棚瀬知明

    近畿化学協会有機金属部会例会 (2018.6.21東京大学)

  • Multinuclear Metal Centers Constrained by Linear Polyphosphines, Focusing on Metal Atom Chains

    T, Tanase

    43rd International Conference on Coordination Chemistry (2018.7.31-8.5, Sendai Japan)

    口頭発表(招待・特別)

  • Multinuclear Metal Centers Constrained by Linear Polyphosphines

    T. Tanase

    12th China-Japan Joint Symposium on Metal Cluster Compounds (2018.10.25-28 Suzhou, China)

    口頭発表(招待・特別)

  • Chiral Octapalladium Chains

    K. Nakamae

    錯体化学会第70回討論会, 2020年09月28日, 2020年09月28日

    口頭発表(招待・特別)

担当経験のある科目(授業)

  • 有機金属クラスター化学Ⅰ (奈良女子大学)

  • 有機金属・錯体化学セミナーA-Ⅰ (奈良女子大学)

  • 無機化学概論Ⅱ (奈良女子大学)

  • 化学キャリアセミナーⅤ (奈良女子大学)

  • 化学キャリアセミナーⅣ (奈良女子大学)

  • 化学キャリアセミナーⅥ (奈良女子大学)

  • 無機化学外国語特論Ⅰ (奈良女子大学)

  • 化学のための物理Ⅰ(a) (奈良女子大学)

  • 有機金属錯体化学 (奈良女子大学)

  • 化学基礎実験1(B) (奈良女子大学)

  • 化学基礎実験1 (奈良女子大学)

  • 基礎化学Ⅲ (奈良女子大学)

  • 機能化学概論 (奈良女子大学)

  • 錯体化学 (奈良女子大学)

  • 化学専門実験1 (奈良女子大学)

  • 化学のための物理Ⅰ (奈良女子大学)

  • 有機金属錯体化学(化学専攻) (奈良女子大学)

  • 機器分析2 (奈良女子大学)

  • エネルギーと化学 (奈良女子大学)

  • 卒業研究2,4(化学科) (奈良女子大学)

  • 卒業研究1,3(化学科) (奈良女子大学)

  • 錯体化学(化学科) (奈良女子大学)

  • 基礎化学III(化学結合論)(化学科) (奈良女子大学)

  • 化学のための物理1(力学)(化学科) (奈良女子大学)

  • 生物無機化学(化学専攻) (奈良女子大学)

  • 卒業研究4(化学科) (奈良女子大学)

  • 有機金属化学(化学科) (奈良女子大学)

  • 固体化学(化学科) (奈良女子大学)

  • 化学基礎実験3(化学科) (奈良女子大学)

  • 基礎化学2(化学科) (奈良女子大学)

  • 機能性錯体化学セミナーIII(化学専攻) (奈良女子大学)

  • 化学セミナー(化学科) (奈良女子大学)

  • 卒業研究3(化学科) (奈良女子大学)

  • 化学専門実験1(化学科) (奈良女子大学)

  • 有機金属化学論演習 (奈良女子大学)

  • 有機金属化学論 (奈良女子大学)

  • 機能性ナノ分子科学演習 (奈良女子大学)

  • 機能性ナノ分子科学 (奈良女子大学)

  • 有機金属化学 (奈良女子大学)

  • 基礎化学4 (奈良女子大学)

  • 基礎化学2 (奈良女子大学)

  • 機能性錯体化学セミナーⅢ (奈良女子大学)

所属学協会

  • 近畿化学協会

  • 錯体化学会

  • 英国王立化学協会

  • 日本化学会

  • 米国化学会



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