Researchers Database

NAKAJIMA Takayuki

FacultyFaculty Division of Natural Sciences Research Group of Chemistry
PositionProfessor
Last Updated :2022/10/06

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Profile and Settings

  • Name (Japanese)

    Nakajima
  • Name (Kana)

    Takayuki

Degree

  • Engineering, Waseda University

Research Interests

  • 超分子化学
  • 錯体化学
  • 有機金属化学
  • Supramolecular Chemistry
  • Coordination Chemistry
  • Organometallic Chemistry

Research Areas

  • Nanotechnology/Materials, Inorganic and coordination chemistry

Research Experience

  • Apr. 2007, Mar. 2012, -:奈良女子大学理学部化学科准教授
  • Apr. 2004, Mar. 2007, :早稲田大学理工学術院応用化学科助手
  • Jan. 2002, Mar. 2004, :エアランゲンニュルンベルグ大学博士研究員
  • Apr. 2001, Dec. 2002, Contract Researcher
  • Apr. 1998, Mar. 2001, Special Postdoctal Researcher
  • Apr. 1995, Mar. 1998, :日本学術振興会特別研究員DC1
  • Apr. 2017, Mar. 2022, 大阪市立大学 非常勤講師
  • Apr. 2012, Mar. 2022, 奈良女子大学研究院自然科学系化学領域 准教授
  • Sep. 1999, Mar. 2000, 東京農工大学 応用化学科 非常勤講師
  • Apr. 2022, 9999, 奈良女子大学研究院自然科学系化学領域 教授

Education

  • Apr. 1995, Mar. 1997, 早稲田大学理工学研究科応用化学専攻博士後期課程
  • Apr. 1993, Mar. 1995, 早稲田大学理工学研究科応用化学専攻修士課程
  • Apr. 1989, Mar. 1993, 早稲田大学理工学部応用化学科

Association Memberships

  • 有機合成化学協会
  • 錯体化学会
  • 日本化学会

Academic Contribution

  • 第51回 有機金属若手の会 夏の学校, Academic society etc, 有機金属若手の会, 02 Jul. 2018, 04 Jul. 2018
  • 錯体化学会第65回討論会, Academic society etc, 錯体化学会, 21 Sep. 2015, 23 Sep. 2015
  • Catalysis and Fine Chemicals 2011, Academic society etc, 触媒学会, 04 Dec. 2011, 08 Dec. 2011

Ⅱ.研究活動実績

Published Papers

  • Refereed, CHEMISTRY-A EUROPEAN JOURNAL, WILEY-V C H VERLAG GMBH, Chiral Dinuclear Eu-III, Tb-III, and Y-III Complexes Supported by P-Stereogenic Linear Tetraphosphine Tetraoxide, Tomoaki Tanase; Kanako Nakamae; Yume Okawa; Mami Hamada; Arimasa Matsumoto; Takayuki Nakajima; Takuya Nakashima; Tsuyoshi Kawai, A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)(4), was synthesized to prepare C-2 dinuclear M(hfa)(3) complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)(3) complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)(2), were also prepared, and comparison of their photophysical properties for the Eu-III complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)(3) units through intramolecular pi-pi stacking constraint in the dinuclear system., Feb. 2022, 28, 8, Scientific journal
  • Refereed, Inorganic Chemistry, American Chemical Society (ACS), Unsymmetric Dinuclear RhI2 and RhIRhIII Complexes Supported by Tetraphosphine Ligands and Their Reactivity of Oxidative Protonation and Reductive Dechlorination, Takayuki Nakajima; Mami Maeda; Aya Matsui; Mariko Nishigaki; Momoko Kotani; Tomoaki Tanase, 17 Jan. 2022, 61, 2, 1102, 1117, Scientific journal
  • Refereed, Chemical Communications, Royal Society of Chemistry (RSC), Electrochemical hydrogen formation catalysed by a Pd8 string, Tomoaki Tanase; Kanako Nakamae; Haruka Miyano; Yoshimi Fujisawa; Yasuyuki Ura; Takayuki Nakajima, The Pd8 string supported by linear tetraphosphine ligands reacted with H+ to afford a Pd4H complex with a terminal hydride, and was applied to the electrocatalytic H2 formation from H+ by making a chemically modified electrode with Nafion film., Oct. 2021, 57, 85, 11264, 11267, Scientific journal
  • Refereed, Chemistry – A European Journal, Wiley, Octapalladium Strings Trap C60 and C70 Fullerenes Affording Metal‐Chain‐Wired Bucky Balls, Tomoaki Tanase; Kanako Nakamae; Yasutaka Kitagawa; Takayuki Nakajima, Reactions of Pd-8 strings supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) ligands, [Pd-8(meso-dpmppm)(4)(L)(2)](4+) (L=CH3CN (1), XylNC (2)) with C-60 resulted in the exclusive formation of unprecedented metal-chain-wired C-60 bucky balls, [{Pd-4(meso-dpmppm)(2)(L)}(2)(C-60)](4+) (L=CH3CN (11), XylNC (12)), in which a C-60 fullerene is trapped in the central Pd-Pd junction, as unambiguously established by spectroscopic, X-ray crystallographic, and theoretical techniques. The similar reaction of Pd-8 strings supported by rac-dpmppm, [Pd-8(rac-dpmppm)(4)(CH3CN)(2)](4+) (3) also afforded a racemic mixture of [{Pd-4((R*,R*)-dpmppm)(2)(CH3CN)}(2)(C-60)](4+) (13) without scrambling the Pd-4 fragments with (R,R)- and (S,S)-dpmppm ligands. Consequently, those of enantiopure chiral Pd-8 strings, [Pd-8((R*,R*)-dpmppm)(4)(CH3CN)(2)](4+), certainly afforded chiral bucky balls of [{Pd-4((R*,R*)-dpmppm)(2)(CH3CN)}(2)(C-60)](4+) (13(RR) and 13(SS)), that exhibit mirror-image circular dichroism spectra. The reactions of 1 and 2 were also applied for trapping a C-70 fullerene to give 2 : 1 adducts of [{Pd-4(meso-dpmppm)(2)(L)}(2)(C-70)](4+) (L=CH3CN (21), XylNC (22)). These results provide useful information for creating a platform to develop dimensionally and chirality controlled metal-carbon nanocomposite materials., 09 Sep. 2021, 27, 51, 12953, 12958, Scientific journal
  • Refereed, Chemistry – A European Journal, Wiley, Fine Tunable, Redox Active Octapalladium Chains Supported by Linear Tetraphosphines, Leading to Dynamically 1D Self‐Assembled Coordination Polymers, Tomoaki Tanase; Kanako Nakamae; Haruka Miyano; Yasuyuki Ura; Yasutaka Kitagawa; Shiho Yada; Tomokazu Yoshimura; Takayuki Nakajima, A series of the octapalladium chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) ligands, [Pd8(meso-dpmppm)4(L)2](BF4)4 (L=none (1), solvents: CH3CN (2 a), dmf (2 b), dmso (2 c), RN≡C: R=Xyl (3 a), Mes (3 b), Dip (3 c), tBu (3 d), Cy (3 e), CH3(CH2)7 (3 f), CH3(CH2)11 (3 g), CH3(CH2)17 (3 h)) and [Pd8(meso-dpmppm)4(X)2](BF4)2 (X=Cl (4 a), N3 (4 b), CN (4 c), SCN (4 d)), were synthesized by using 2 a as a stable good precursor, and characterized by spectroscopic (IR, 1H and 31P NMR, UV-vis-NIR, ESI-MS) measurements and X-ray crystallographic analyses (for 1, 2 a, b, 3 a, b, e, f, 4 a–d). On the basis of DFT calculations on the X-ray determined structure of 2 b ([2b-Pd8]4+) and the optimized models [Pd8(meso-Ph2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ([Pd8Ph8]4+) and [Pd8(meso-H2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ([Pd8H8]4+), with and without empirically calculating dispersion force stabilization energy (B3LYP-D3, B3LYP), the formation energy between the two Pd4 fragments is assumed to involve mainly noncovalent interactions (ca. −70 kcal/mol) with four sets of interligand C−H/π interactions and Pd⋅⋅⋅Pd metallophilic one, while electron shared covalent interactions are almost canceled out within the Pd8 chain. All the compounds isolated are stable in solution and exhibit characteristic absorption at ∼900 nm, which is assignable to a spin allowed HOMO to LUMO transition, and shows temperature dependent intensity change with variable absorption coefficients presumably due to coupling with some thermal vibrations. The structures and electronic states of the Pd8 chains are found finely tunable by varying the terminal capping ligands. In particular, theoretical calculations elucidated that the HOMO-LUMO energy gap is systematically related to the central Pd−Pd distance (2.7319(6)–2.7575(6) Å) by two ways with neutral ligands L (1, 2, 3) and with anionic ligands X (4), which are reflected on the NIR absorption energy of 867–954 nm. The isocyanide terminated Pd8 complexes (3) further reacted with excess of RNC (6 eq) to afford the Pd4 complexes, [Pd4(meso-dpmppm)2(RNC)2](BF4)2 (13), and the cyclic voltammograms of 2 a (L=CH3CN), 3, and 13 (R=Xyl, Mes, tBu, Cy) demonstrated wide range redox behaviors from 2{Pd4}4+ to 2{Pd4}0 through 2{Pd4}2+↔{Pd8}4+, {Pd8}3+, and {Pd8}2+ strings. The oxidized complexes, [Pd4(meso-dpmppm)2(RNC)3](BF4)4 (16), were characterized by X-ray analyses, and the two-electron reduced chain of [Pd8(meso-dpmppm)4](BF4)2 (7) was analyzed by spectroscopic and electrochemical techniques and DFT calculations. Reactions of 2 a with 1 equiv. of aromatic linear bisisocyanide (BI) in CH2Cl2 deposited insoluble coordination polymers, {[Pd8(meso-dpmppm)4(BI)](BF4)4}n (5), and interestingly, they were soluble in acetonitrile, 31P{1H} and 1H DOSY NMR spectra as well as SAXS curves suggesting that the coordination polymers may exist in acetonitrile as dynamically 1D self-assembled coordination polymers comprising ca. 50 units of the Pd8 rod averaged within the timescale., 19 Aug. 2021, 27, 47, 12078, 12103, Scientific journal
  • Refereed, Journal of Organometallic Chemistry, Elsevier BV, 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, A linear tetraphosphine, meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm), was found to support a series of bent tetranuclear rhodium(I) arrays of [Rh4(μ−Cl)Cl2(CO)4(meso-dpmppm)2]Cl (1), [Rh4(μ−Cl)2(meso-dpmppm)2]X2 (X = PF6 (2a), BF4 (2b), TfO (2c), BPh4 (2d)), and [Rh4(μ−Cl)(CH3CN)2(CO)4(meso-dpmppm)2](TfO)3 (3) which are regarded as tetranuclear extended Vaska-type RhI complexes. Two meso-dpmppm ligands with mutual syn-arrangement established a flexible bending chains of {Rh4(meso-dpmppm)2}4+ which accommodated a variety of ligand sets of {(μ−Cl)Cl2(CO)4}3‒, {(μ−Cl)2(CO)4}2‒, and {(μ−Cl)(CH3CN)2(CO)4}‒ with Rh–Rh–Rh angles of 142.18(1)–161.54(1)°. The tetranuclear rhodium(I) core of 2 was interestingly reactive toward H2 (1 atm) under mild conditions at room temperature to afford {Rh4H3}3+ hydride complexes with linear RhI∙∙∙RhII–RhII∙∙∙RhI array, [Rh4(μ−Cl)2(μ−H)3(μ−CO)(CO)2(meso-dpmppm)2]X (X = PF6 (4a), BF4 (4b), TfO (4c)), where the positions of three hydride ligands were estimated with 1H, 1H{31P}, and 31P{1H} NMR spectra, a single crystal X-ray diffraction analysis, and DFT calculations. The linearly ordered {Rh4H3}3+ species that store four electrons from dihydrogen molecules is the first example of linear Rh hydride chains and would be useful platform for exploring cooperative reactions promoted by constrained multimetallic centers., May 2021, 939, 121771, 121771, Scientific journal
  • Refereed, Inorganic Chemistry, American Chemical Society (ACS), 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, Binuclear Pd(II) and Pt(II) complexes supported by rac-dpmppm (bis[(diphenylphosphinomethyl)phenylphosphino]methane) in a triply-bridged Z-form, [M2Cl4(rac-dpmppm)] (M = Pd (3a), Pt (3b)), readily reacted with 2,6-xylyl isocyanide (XylNC) in the presence of NH4PF6 to afford [M2Cl2(rac-dpmppm)(XylNC)2](PF6)2 (M = Pd (4a), Pt (4b)), in which each metal center accommodates one isocyanide ligand at the trans position to the inner P atom of dpmppm. Similarly, treatment of 3a and 3b with axially chiral (R/S)-1,1′-binaphthyl-2,2′-bisisocyanide (rac-Binac) in the presence of NH4OTf gave cyclic tetranuclear complexes, [{M2Cl2(rac-dpmppm)(rac-Binac)}2](OTf)4 (M = Pd (5), Pt (8)), where two {M2Cl2(rac-dpmppm)}2+ fragments are connected by two rac-Binac ligands through chirality sorting of (R*,R*)-dpmppm and (R*)-Binac. Complex 5 could be transformed into the halide exchanged tetranuclear complexes, [{Pd2X2(rac-dpmppm)(rac-Binac)}2](OTf)4 (X = Br (6), I (7)), to show that the rectangular arrangement of four Pd(II) ions is elongated by repulsive interaction between halide ligands. By using (R)- and (S)-Binac, enantiopure Pd4 complexes, [{Pd2Cl2((R*,R*)-dpmppm)((R*)-Binac)}2](OTf)4 (5RR/R and 5SS/S), were successfully isolated as pure crystalline forms, from which enantiopure (R,R)- and (S,S)-dpmppm were obtained by treatment with NaCN aqueous solution. Namely, optical resolution of rac-dpmppm was established through the tetranuclear Pd complexes, which is the first example for methylene-bridged polyphosphines, R2P(CH2PR)nCH2PR2 (n > 0). Furthermore, chiral octapalladium chains, [Pd8((R*,R*)-dpmppm)4(NCCH3)2](BF4)4 (2RR and 2SS), were synthesized by reacting enantiopure P-chiral dpmppm with [Pd2(CH3CN)6](BF4)2 and [Pd2(dba)3]·C6H6 and were characterized by spectroscopic and X-ray crystallographic analyses, to determine the absolute configurational structures. The Pd8 chains are the longest enantiopure chiral single-metal-atom chains structurally characterized, thus far, and the electronic structures were examined on the basis of DFT calculations of 2RR., 01 Mar. 2021, 60, 5, 3259, 3273, Scientific journal
  • Refereed, Journal of Organometallic Chemistry, Elsevier BV, 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., Oct. 2020, 925, 121488, 121488, Scientific journal
  • Refereed, European Journal of Inorganic Chemistry, Wiley, Multinuclear Copper Hydride Complexes Supported by Polyphosphine Ligands, Takayuki Nakajima; Kanako Nakamae; Yasuyuki Ura; Tomoaki Tanase, 23 Jun. 2020, 2020, 23, 2211, 2226, Scientific journal
  • Refereed, Chemistry Letters, The Chemical Society of Japan, Transition Metal Clusters Constrained by Linear Tetradentate Phosphine Ligands, Takayuki Nakajima; Tomoaki Tanase, 05 Apr. 2020, 49, 4, 386, 394, Scientific journal
  • Refereed, Angewandte Chemie International Edition, Wiley, Facially Dispersed Polyhydride Cu 9 and Cu 16 Clusters Comprising Apex‐Truncated Supertetrahedral and Square‐Face‐Capped Cuboctahedral Copper Frameworks, Kanako Nakamae; Takayuki Nakajima; Yasuyuki Ura; Yasutaka Kitagawa; Tomoaki Tanase, 03 Feb. 2020, 59, 6, 2262, 2267, Scientific journal
  • Refereed, Eur. J. Inorg. Chem., Wiley, Dinuclear Copper Complexes Triply Bridged by a Tetraphosphine, rac-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2, T. Tanase; R. Otaki; A. Okue; K. Nakamae; T. Nakajima, Aug. 2019, 2019, 37, 3993, 4005, Scientific journal
  • Refereed, Dalton Trans, Tetra-, hexa-and octanuclear copper hydride complexes supported by tridentate phosphine ligands, T. Nakajima; K. Nakamae; R. Hatano; K. Imai; M. Harada; Y. Ura; T. Tanase, © 2019 The Royal Society of Chemistry. Multinuclear copper hydride complexes were synthesized by using a triphosphine, bis(diphenylphosphinomethyl)phenylphosphine (dpmp). The reaction of [Cu(MeCN)4]PF6 with dpmp in 2:1 ratio in the presence of Me4NBH4 or NaBH4 yielded a hexanuclear complex, [Cu6(μ3-H)5(μ-dpmp)3]PF6 (1), together with a minor product [Cu8(μ-H)2(μ4-H)4(μ-dpmp)4](PF6)2 (2) in a very low yield. Complex 1 was also prepared from [CuH(PPh3)]6, [Cu(MeCN)4]PF6, and dpmp in 87%, but the yield of 2 could not be improved presumably due to its instability in solution. A tetranuclear complex, [Cu4(μ-H)(μ3-H)2(μ-dpmp)3]PF6 (4), was obtained from the reaction of [Cu(MeCN)4]PF6 with dpmp in 4:3 ratio, or that of [Cu3(μ-dpmp)2(MeCN)4](PF6)3 (3) and dpmp, in the presence of Me4NBH4 for both cases. The structures of 1, 2, and 4 were determined by X-ray crystallography, and the positions of hydride ligands were elucidated by DFT optimization. Complex 1 consists of a distorted trigonal anti-prismatic Cu6 core bridged by three L-shaped dpmp ligands and five μ3-hydrides, and 2 is composed of three edge-shared tetrahedral Cu4 units supported by four L-shaped dpmp ligands and two μ2-hydrides in the two outer Cu4 units and four μ4-hydride ligands in the central Cu4 units. The structures of two outer Cu4 units in 2 resemble those of 4, where a Cu4 tetrahedron is supported by two L-shaped dpmp ligands and one dpmp-κ2P,P′ bridge, in addition to one μ2- and two μ3-hydrides. Natural bond orbital analyses suggest that the hydrides act as glue between the multinuclear copper centres through electron-deficient delocalized bonding interactions, which result in partial electron migration from hydrides to CuI centres., Jul. 2019, 48, 32, 12050, 12059, Scientific journal
  • Refereed, J. Am. Chem. Soc., Synergistic Cu2 Catalysts for Formic Acid Dehydrogenation, T. Nakajima; Y. Kamiryo; M. Kishimoto; K. Imai; K. Nakamae; Y. Ura; T. Tanase, © 2019 American Chemical Society. Hexanuclear copper hydride complexes, [Cu6(μ3-H)2(meso-L4)3(RNC)4](PF6)4 (R = tBu (6a), Cy (6b)), were prepared by using a new linear tetraphosphine, meso-Ph2PCH2P(Ph)(CH2)4P(Ph)CH2PPh2 (meso-L4), and were converted into active catalysts of [Cu2(μ-O2CH)(meso-L4)(RNC)2]+ under the reaction conditions of formic acid dehydrogenation, where unsymmetric dinuclear copper sites supported by the tetradentate phosphine and isocyanide ligands were essential to demonstrate effective catalytic activity., May 2019, 141, 22, 8732, 8736, Scientific journal
  • Refereed, Chem. Eur. J., Alloyed Tetranuclear Metal Chains of Pd4-nPtn (n = 0-3) Scaffolded by a New Linear Tetraphosphine Containing a PNP Bridge, T. Tanase; M. Tanaka; M. Hamada; Y. Morita; K. Nakamae; Y. Ura; T. Nakajima, © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim A new linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd4−nPtn(μ-rac-dpmppan)2(XylNC)2](PF6)2 (XylNC=xylyl isocyanide; n=0: Pd4 (1), 1: PtPd3 (2), 2: PtPd2Pt (3), 2: Pt2Pd2 (4), 3: Pt2PdPt (5)), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The 31P{1H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1–5 exhibited characteristic bands at 635–510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dσ*σσ*) to LUMO (dσ*σ*σ*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd4 chain., Apr. 2019, 25, 35, 8219, 8224, Scientific journal
  • Refereed, J. Organomet. Chem., Elsevier BV, Synthesis and characterization of iridium hydride complexes with meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an unsymmetric pincer ligand, T. Tanase; N. Mori; K. Nakamae; T. Nakajima, Mar. 2019, 888, 54, 64, Scientific journal
  • Refereed, J. Organomet. Chem., Elsevier BV, 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, T. Tanase; M. Urabe; H. Takenaka; K. Nakamae; T. Nakajima, Jan. 2019, 883, 41, 46, Scientific journal
  • Refereed, Inorg. Chem., Tri- and Tetranuclear Copper Hydride Complexes Supported by Tetradentate Phosphine Ligands, T. Nakajima; Y. Kamiryo; K. Hachiken; K. Nakamae; Y. Ura; T. Tanase, Copyright © 2018 American Chemical Society. Three types of tetradentate phosphine ligands with different central methylene chains and configurations, meso- and rac-Ph2PCH2P(Ph)(CH2)nP(Ph)CH2PPh2 (n = 2, meso- and rac-dpmppe; n = 3, meso-dpmppp) were utilized to synthesize a new series of tri- and tetranuclear copper hydride complexes. Reactions of meso-dpmppe or meso-dpmppp with CuCl/NH4PF6 or [Cu(CH3CN)4]PF6 in the presence of NaBH4 afforded trinuclear copper hydride complexes, [Cu3(μ3-H)(meso-dpmppe)2](PF6)2 (1) and [Cu3(μ3-H)(meso-dpmppp)2](PF6)2 (2), while a similar reaction with rac-dpmppe resulted in the formation of a tetranuclear copper dihydride complex, [Cu4(μ3-H)2(rac-dpmppe)2](PF6)2 (5). Complexes 1 and 5 further reacted with RNC (R = tBu, Cy, Xyl) to give [Cu3(μ3-H)(meso-dpmppe)2(XylNC)](PF6)2 (3), [Cu4(μ3-H)2(meso-dpmppe)2(RNC)2](PF6)2 (R = tBu (4a), Cy (4b)) and [Cu4(μ3-H)2(rac-dpmppe)2(RNC)2](PF6)2 (R = tBu (6a), Cy (6b), Xyl (6c)), respectively. Complexes 1-6 were characterized by ESI-MS and 1H and 31P NMR spectroscopy and X-ray diffraction analyses, demonstrating that a hydride ligand is located at the center of triangular Cu3 plane of 1-3, while two μ3-hydride-capped Cu3 planes are fused to result in rhombic Cu4H2 structures in 4a,b, 5, and 6a-c. Complexes 1-6 in CD3CN solutions notably showed high thermal stability and no reactivity toward H2O and CO2. DFT calculations indicated an interesting correlation between the Wiberg bond indices (WBI) of Cu-H bonds and their natural atomic charge (NAC), where the isocyanide ligands had an appreciable influence on the Cu-H interactions., Sep. 2018, 57, 17, 11005, 11018, Scientific journal
  • Refereed, J. Organomet. Chem., Elsevier BV, N-Acyclic carbene complexes supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) as an asymmetric pincer ligand, T. Tanase; M. Urabe; N. Mori; S. Hatada; S. Noda; H. Takenaka; K. Nakamae; T. Nakajima, Aug. 2018, 878, 45, 59, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, 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., Sep. 2017, 35, 4097, 4109, Scientific journal
  • Refereed, CHEMISTRY-A EUROPEAN JOURNAL, WILEY-V C H VERLAG GMBH, 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., Jul. 2017, 23, 40, 9457, 9461, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, 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., Mar. 2017, 11, 1422, 1426, Scientific journal
  • Refereed, CHEMISTRY-A EUROPEAN JOURNAL, WILEY-V C H VERLAG GMBH, 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., Jan. 2017, 23, 3, 524, 528, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, 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., Oct. 2016, 28, 4701, 4710, Scientific journal
  • Refereed, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER SCIENCE SA, 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., Jul. 2016, 814, 35, 41, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, 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., Jun. 2016, 17, 2764, 2773, Scientific journal
  • Refereed, DALTON TRANSACTIONS, ROYAL SOC CHEMISTRY, 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, 45, 11, 4747, 4761, Scientific journal
  • Refereed, DALTON TRANSACTIONS, ROYAL SOC CHEMISTRY, 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, 45, 17, 7209, 7214, Scientific journal
  • Refereed, CHEMISTRY-AN ASIAN JOURNAL, WILEY-V C H VERLAG GMBH, 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., Dec. 2015, 10, 12, 2618, 2622, Scientific journal
  • Refereed, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER SCIENCE SA, 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., Nov. 2015, 797, 37, 45, Scientific journal
  • Refereed, INORGANIC CHEMISTRY, AMER CHEMICAL SOC, 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., Sep. 2015, 54, 17, 8298, 8309, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, Synthesis, Magnetic Properties, and X-ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [M-4(II)(HL2)(4)(OAc)(4)], Andreas Scheurer; Jana Korzekwa; Takayuki Nakajima; Frank Hampel; Anna Buling; Christine Derks; Manfred Neumann; Loic Joly; Konstantin Petukhov; Klaus Gieb; Paul Mueller; Karsten Kuepper; Karsten Meyer, Under anaerobic conditions, the reactions of cobalt(II) and nickel(II) acetate tetrahydrate with 2,6-pyridinedimethanol (H2L2, 3) in anhydrous acetonitrile afforded two tetranuclear metal(II) complexes [M-4(II)(HL2)(4)(OAc)(4)] (4; M-II = Co2+, Ni2+) with a [M-4(mu(3)-O)(4)](4+) cubane core. X-ray structural analyses revealed that both MII cubanes 4a center dot 2CH(3)OH and 4b center dot 2CH(3)OH are isostructural and crystallize in the tetragonal space group I4(1)/acd with eight molecules in the unit cell. In the solid state, the orientation of the cubane cores of 4 and the formation of a 3D framework were controlled by pi-pi interactions as well as intra- and intermolecular O-H center dot center dot center dot O hydrogen bonds. Variable-temperature magnetic susceptibility measurements revealed that the cubanes 4 show a ferrimagnetic coupling scheme that leads to a diamagnetic ground state for both complexes. Core-level X-ray photoelectron spectroscopy confirmed that the Co and Ni ions in 4a and 4b are in a divalent state. X-ray magnetic circular dichroism was performed to extract the spin and orbital contributions to the Co and Ni magnetic moments. We compared the experimental results of the local electronic structures around the Co2+ ions in 4a and the Ni2+ ions in 4b with charge-transfer multiplet simulations., Apr. 2015, 11, 1892, 1901, Scientific journal
  • Refereed, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, WILEY-V C H VERLAG GMBH, 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., Jan. 2015, 54, 3, 1016, 1021, Scientific journal
  • Refereed, CHEMISTRY-AN ASIAN JOURNAL, WILEY-V C H VERLAG GMBH, 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., Nov. 2014, 9, 11, 3106, 3110, Scientific journal
  • Refereed, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER SCIENCE SA, 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., Oct. 2014, 768, 61, 67, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, 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., Oct. 2014, 29, 5021, 5033, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, Systematic Heterodinuclear Complexes with MM '(mu-meppp) Centers That Tune the Properties of a Nesting Hydride (M = Ni, Pd, Pt; M ' = Rh, Ir; H(2)meppp = 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., Aug. 2014, 33, 15, 3950, 3965, Scientific journal
  • Refereed, CHEMISTRY LETTERS, CHEMICAL SOC JAPAN, 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., Jun. 2014, 43, 6, 913, 915, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, 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., Apr. 2014, 33, 8, 1893, 1904, Scientific journal
  • Refereed, CHEMISTRY-A EUROPEAN JOURNAL, WILEY-V C H VERLAG GMBH, 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., Feb. 2014, 20, 6, 1577, 1596, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, 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., Dec. 2013, 32, 24, 7470, 7477, Scientific journal
  • Refereed, Chem. Commun., Reversible dioxygen binding on asymmetric dinuclear rhodium centres, T. Nakajima; M. Sakamoto; S. Kurai; B. Kure; T. Tanase, Apr. 2013, 49, 5239, 5338, Scientific journal
  • Refereed, J. Organomet. Chem., Synthesis and structure of a dinuclear NiIIIrIII hydride complex supported by a N3S2 bridging ligand: Comparison of property and reactivity of dinuclear NiII(H)MIII units (M = Rh, Ir) in aqueous media, B. Kure; T. Nakajima; T. Tanase, Mar. 2013, 733, 28, 35, International conference proceedings
  • Refereed, DALTON TRANSACTIONS, ROYAL SOC CHEMISTRY, 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, 42, 45, 15941, 15952, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, 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., Dec. 2012, 31, 24, 8482, 8497, Scientific journal
  • Refereed, INORGANIC CHEMISTRY, AMER CHEMICAL SOC, 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., Nov. 2012, 51, 22, 12503, 12510, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, 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., Jul. 2012, 31, 13, 4791, 4800, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, 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., Jun. 2012, 31, 11, 4283, 4294, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, 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., Jan. 2012, 31, 1, 133, 143, Scientific journal
  • Refereed, INORGANICA CHIMICA ACTA, ELSEVIER SCIENCE SA, 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., Dec. 2011, 379, 1, 100, 108, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, 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)., Nov. 2011, 30, 22, 6063, 6066, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, 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., Oct. 2011, 28, 4325, 4330, Scientific journal
  • Refereed, CHEMISTRY-A EUROPEAN JOURNAL, WILEY-V C H VERLAG GMBH, Stepwise Construction of Au4Ag2Cu2 Coinage Rings Supported by Linear Tetraphosphine Ligands, Yukie Takemura; Tomoko Nishida; Bunsho Kure; Takayuki Nakajima; Masayasu Iida; Tomoaki Tanase, Sep. 2011, 17, 38, 10528, 10532, Scientific journal
  • Refereed, 安定同位体と生体ガス医学応用, 日本安定同位体・生体ガス医学応用学会, Syntheses of stable carbon isotope multi-labeled α-amino acids and 5-aminolevulinic acids, 末木 俊輔; 上原 悠介; 飯泉 礼子; 小林 祥一朗; 趙 依文; 中島 隆行; 清水 功雄, 2010, 2, 1, 29, 34, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, 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), Nov. 2009, 32, 4820, 4829, Scientific journal
  • Refereed, DALTON TRANSACTIONS, ROYAL SOC CHEMISTRY, 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, 46, 10231, 10243, Scientific journal
  • Refereed, CHEMICAL COMMUNICATIONS, ROYAL SOC CHEMISTRY, 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, 13, 1664, 1666, Scientific journal
  • Refereed, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, WILEY-V C H VERLAG GMBH, Hexa- and Octagold Chains from Flexible Tetragold Molecular Units Supported by Linear Tetraphosphine Ligands, Yukie Takemura; Hiroe Takenaka; Takayuki Nakajima; Tomoaki Tanase, 2009, 48, 12, 2157, 2161, Scientific journal
  • Refereed, CHEMISTRY LETTERS, CHEMICAL SOC JAPAN, Phosphine-dependent stereoselective nucleophilic reaction to bicyclic bis-mu-dichloro-eta(3)-allylpalladium complexes, Ryohei Ogawa; Takayuki Nakajima; Isao Shimizu, The effects on ligands in nucleophilic reaction of eta(3)-allylpalladium chloride dimers were studied. Reaction of steroid 1 with Na2PdCl4 in concentrated HCl under CO gave the cis,trans-bis-mu-dichloro-eta(3)-allylpalladium complex 2 after recrystallization. Reaction of 2 with malonate anion in the presence of PPh3 afforded trans-3 in 65% yield. When Dppe was used, cis-3 was obtained as the major product. In nucleophilic reactions of bicyclic eta(3)-allylpalladium chloride complex 4a or 4b with PPh3, cis-5 was the major product. However, the reaction with Dppe gave trans-5 predominantly. The stereochemistry in the nucleophilic reaction of eta(3)-allylpalladium chloride dimer is dependent on the added phosphines., Mar. 2008, 37, 3, 278, 279, Scientific journal
  • Refereed, CHEMISTRY LETTERS, CHEMICAL SOC JAPAN, Enantioselecitve elimination of Pd-H from eta(3)-allylpalladium-Tol BINAP complexes. Evidence of syn elimination pathway, Ryohei Ogawa; Yusuke Shigemori; Koichi Uehara; Jiro Sano; Takayuki Nakajima; Isao Shimizu, The palladium-catalyzed elimination of the bicyclic cis-acetate 1b using Pd catalyst and (R)-p-Tol BINAP gave the (S)-diene 2 with 58% ee. Bicyclic eta(3)-allylpalladium complex 3a with (R)-p-Tol BINAP, considered as an intermediate in the catalytic reaction from 1b, was prepared. Enantioselectivity in decomposition of 3a is dependent on the reaction conditions. The thermal decomposition of 3a without base gave the (S)-2 with 70% ee. However, the decomposition of 3a in the presence of excess base gave (R)-2 with 58% ee. Syn elimination from 3a was found to proceed preferentially from the decomposition results of the deuterium-labeled complexes., Nov. 2007, 36, 11, 1338, 1339, Scientific journal
  • Refereed, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER SCIENCE SA, Reactivities governed by a single metal atom M in mixed-metal highnuclearity clusters having [Ru5M(C)] core (M = Co, Rh, Pd): Site-nonselective, site-selective, and chemo-selective variations in the SO2-trapping reactions, Takayuki Nakajima; Hiromi Konomoto; Haruo Ogawa; Yasuo Wakatsuki, The SO2 substitution for a CO ligand of the hexa-nuclear carbonyl complexes having Ru5M(C) type carbido-metal core, [PPN][Ru5CO(C)(CO)(16)] (2), [PPN][Ru5Rh(C)(CO)(16)] (3), and Ru5Pd(C)(CO)(16) (4), is dramatically affected by the kind of metal atom M: 2 (M = Co) is reactive but not site-selective, 3 (M = Rh) is reactive and site-selective, whereas 4 (M = Pd) is not reactive at all even though 4 can easily react with PPh3 to give the substitution products. (C) 2007 Elsevier B.V. All rights reserved., Oct. 2007, 692, 22, 4886, 4894, Scientific journal
  • Refereed, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER SCIENCE SA, Synthesis of three-component high nuclearity cluster complexes with ruthenium carbido carbonyl clusters as a building block, Takayuki Nakajima; Hiromi Konomoto; Haruo Ogawa; Yasuo Wakatsuki, Treatment of AgNO3 with the Rh-Ru and Cu-Ru hetero bimetallic clusters, [PPN][RhRu5C(CO)(14)(cod)] and [PPh4](2)[CuRu6C(CO)(16)Cl], afforded novel three-component complexes having one silver-, and two silver-bridges between respective cluster units, [PPN]{Ag[RhRu5C(CO)(14)(cod)](2)} and [PPh4](2){Ag-2[CuRu6C(CO)(16)Cl](2)), respectively. Reaction of the ruthenium-copper cluster [PPh4](2) (Cu-4[Ru6C(CO)(16)]2Cl(2)} (6) with Pd-2(dba)(3)center dot CHCl3 gave another three-component cluster [PPh4](2) {Cu4Pd2[Ru6C(CO)(16)](2)Cl-2} by incorporation of two palladium atoms. However, a similar reaction of 6 with Pt(dba)(2) gave only a two-component cluster complex, [PPh4](2){Pt-2[Ru6C(CO) (15)](2)}, while the reaction of silver analog [PPN](2){Ag-4[Ru6C(CO)(16)](2)Cl-2} with Pd-2(dba)(3)center dot CHCl3 resulted in the formation of known ruthenium-palladium cluster [PPN](2){Pd-4[Ru6C(CO)(16)](2)}. Treatment of 6 with [RhCl(CO)(2)](2) gave two two-component clusters, [PPh4][RhRu5C(CO)(16)] and [PPh4](2){Cu-7[Ru6C(CO)(15)](2)Cl-3). All the new mixed-metal high nuclearity clusters have been characterized by single crystal X-ray analyses. @ 2007 Elsevier B.V. All rights reserved., Oct. 2007, 692, 22, 5071, 5080, Scientific journal
  • Refereed, JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS, JOHN WILEY & SONS LTD, Synthesis of isotope-labelled [1-C-13]-amino acids from (CO2)-C-13, Takayuki Nakajima; Kazuki Nakayama; Isao Shimizu, Apr. 2007, 50, 5-6, 622, 623, Scientific journal
  • Refereed, INORGANIC CHEMISTRY, AMER CHEMICAL SOC, Synthesis, redox, and magnetic properties of a neutral, mixed-valent heptanuclear manganese wheel with S=27/2 high-spin ground state, Rolf W. Saalfrank; Andreas Scheurer; Raju Prakash; Frank W. Heinemann; Takayuki Nakajima; Frank Hampel; Roland Leppin; Bernd Pilawa; Holger Rupp; Paul Mueller, Reaction of lithium tetrachloromanganate(II) with N-n-butyldiethanolamine H2L3 (3) in the presence of LiH leads to the formation of wheel-shaped, mixed-valent heptanuclear, neutral complex {Mn-II subset of[(Mn2Mn4Cl6)-Mn-II-Cl-III(L-3)(6)]} (4). The manganese wheel crystallizes in the triclinic space group P (1) over bar as 4 center dot 2CHCl(3) or 4 center dot 3THF when either diethyl ether or n-pentane was allowed to diffuse into solutions of 4 in chloroform or tetrahydrofuran. The oxidation states of each manganese ion in 4 center dot 2CHCl(3) or 4 center dot 3THF were assigned on the basis of detailed symmetry, bond length, and charge considerations, as well as by the Jahn-Teller axial elongation observed for the manganese(III) ions, and were further supported by cyclic voltammetry. The analysis of the SQUID magnetic susceptibility data for complex 4 center dot 2CHCl(3) showed that the intramolecular magnetic coupling of the manganese(II,III) ions is dominated by ferromagnetic exchange interactions. This results in an S = 27/2 ground-state multiplet at low magnetic field. At fields higher than 0.68 T, the energetically lowest state is given by the m(S) = 31/2 component of the S = 31/2 multiplet due to the Zeeman effect. The ligand-field-splitting parameters were determined by anisotropy SQUID measurements on single crystalline samples along the crystallographic x, y, and z axes (D = -0.055 K, E = 6.6 mK) and by high-frequency electron spin resonance measurements on a polycrystalline powder of 4 center dot 2CHCl(3) (D = -0.068 K, E = 9.7 mK). The resulting barrier height for magnetization reversal amounts to U approximate to 10 K. Finally, 2DEG Hall magnetization measurements revealed that 4 center dot 2CHCl(3) shows single-molecule magnet behavior up to the blocking temperature of about 0.6 K with closely spaced steps in the hysteresis because of the quantum tunneling of the magnetization., Mar. 2007, 46, 5, 1586, 1592, Scientific journal
  • Refereed, Heterocycles, Short Step Synthesis of Natural 2-Arylquinolones Based on Iridium-Catalyzed Three-Component Coupling Quinoline Synthesis, T. Nakajima; T. Inada; I. Shimizu, Jul. 2006, 69, 497, 504, Scientific journal
  • Refereed, CHEMISTRY LETTERS, CHEMICAL SOC JAPAN, Synthesis of beta-amino ketones by iridium(III)-catalyzed direct-Mannich reaction, Shunsuke Sueki; Takeyuki Igarashi; Takayuki Nakajima; Isao Shimizu, The direct-Mannich reaction of ketones 1, aldehydes 2, and anilines 3 was studied using catalytic amount of transition-metal complexes. The trivalent iridium complex, [IrCl2(H)(cod)](2), catalyzed the direct-Mannich reaction effectively to give various beta-amino kenotes in good yields under mild conditions., Jun. 2006, 35, 6, 682, 683, Scientific journal
  • Refereed, Bulletin of the Chemical Society of Japan, Facile three-component synthesis of substituted quinolines catalyzed by iridium(III) complex, Takayuki Nakajima; Takashi Inada; Takeyuki Igarashi; Tadashi Sekioka; Isao Shimizu, A convenient and efficient synthesis of substituted quinolines via a simple one-pot reaction of an aniline, an aromatic aldehyde, and an enolizable aliphatic aldehyde in the presence of the iridium catalyst [IrCl 2H(cod)]2 under oxygen as an oxidant was developed. The reaction proceeds with Mannich-type imine formation followed by nucleophilic addition to give β-amino aldehydes. Dehydrative cyclization takes place to give dihydroquinoline, which is then dehydrogenated by aerobic oxidation to give 2-aryl-3-alkylquinolines. Dialkylquinolines were obtained by the reaction with anilines and aliphatic aldehydes in good yields. © 2006 The Chemical Society of Japan., 2006, 79, 12, 1941, 1949, Scientific journal
  • Refereed, Heterocycles, One-step synthesis of ethyl quinaldates by lewis acid catalyzed three-component coupling reaction of aromatic amines, aliphatic aldehydes and ethyl glyoxylate, Takashi Inada; Takayuki Nakajima; Isao Shimizu, A convenient, efficient and simple one-pot method for the synthesis of quinaldates was developed by three-component coupling reaction of an arylamine (1), ethyl glyoxylate and an aliphatic aldehyde (2) in the presence of Lewis acid catalyst. The reaction proceeded most effectively using Yb(OTf)3 as a catalyst. © 2005 The Japan Institute of Heterocyclic Chemistry., 31 Dec. 2005, 66, 1, 611, 619, Scientific journal
  • Refereed, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, WILEY-V C H VERLAG GMBH, Syntheses and properties of metal-centered mixed-valent [NEt4]{Mn-II subset of[(Mn3Mn3Cl6)-Mn-II-Cl-III(L)6]} manganese wheels, RW Saalfrank; T Nakajima; N Mooren; A Scheurer; H Maid; F Hampel; C Trieflinger; N Daub, Upon reaction of N-substituted diethanolamines H2L2-4 (4,6, 7) with cesium carbonate and bis(tetraethylammonium) tetrachloromanganate(II) in acetonitrile in the presence of air, the metal-centered mixed-valent manganese wheels [NEt4]{Mn-II subset of[(Mn3Mn3Cl6)-Mn-II-Cl-III(L2-4)(6)]} (8-10) were generated. X-ray crystallographic structure analyses revealed, that 8-10 are principally isostructural and consist of an alternating ring of three Mn-II and three Mn-III ions, centered by an additional Mn-II ion. The cyclic voltammograms of 8 and 10 displayed three quasi-reversible oxidation processes, which are attributed to the subsequent one electron-oxidations of the three peripheral Mn-II ions to Mn-III. Oxidation of the central Mn-II ion is not observed within the applied potential. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)., Mar. 2005, 6, 1149, 1153, Scientific journal
  • Refereed, CHEMISTRY LETTERS, CHEMICAL SOC JAPAN, One-pot synthesis of substituted quinolines by iridium-catalyzed three-component coupling reaction, T Igarashi; T Inada; T Sekioka; T Nakajima; Shimizu, I, A convenient and efficient synthesis of substituted quinolines in a simple one-pot reaction of an arylamine 1, an aromatic aldehyde or aliphatic aldehyde 2 and an aliphatic aldehyde 3 in the presence of transition metal complexes or Lewis acids was developed. Among them, the iridium catalyst [Ir(cod)Cl](2) catalyzed the reaction most efficiently., Jan. 2005, 34, 1, 106, 107, Scientific journal
  • Refereed, INORGANIC CHEMISTRY, AMER CHEMICAL SOC, Six-membered metalla-coronands. Synthesis and crystal packing: Columns, compartments, and 3D-networks, RW Saalfrank; C Deutscher; S Sperner; T Nakajima; AM Ako; E Uller; F Hampel; FW Heinemann, Reaction of various N-substituted diethanolamines H2L3 (4) with calcium hydride and iron(III) chloride leads to the self-assembly of six-membered ferric wheels [Fe6X6(L-3)(6)] (5). Principally, all the iron coronands are isostructural; however, they differ fundamentally with respect to their crystal packing. Exemplarily, this is discussed for selected members of the space groups R(3)over bar, P(3)over bar, P2(1)/c, P2(1)/n, C2/c, and P(1)over bar. Depending on the nature of their sidearms, the ferric wheels create various substructures. For instance, the ferric wheels 5a-i of space group R(3)over bar or P(3)over bar are piled in parallel in cylindrical columns, which are surrounded by six parallel columns alternately dislocated by 1/3c and 2/3 c against the central one. Pronounced van der Waals interactions give rise to compartmentation and incarceration of guest molecules as seen for 5e,g. However, in 5h strong pi-pi interactions create a three-dimensional scaffold, The most significant difference of the ferric wheels 5j-p of space groups P2(1)/c, P2(1/)n, and C2/c is that these ferric wheels are arranged in parallel in two orientations. They differ mainly only by the included angle of the two groups of parallel wheels. In the case of 51, molecular chains are formed in the crystal due to pi-pi interactions. The ferric wheels 5q-y of space group P(1)over bar are packed in the crystal most simply, with all the ferric wheels piled in parallel., Jul. 2004, 43, 14, 4372, 4382, Scientific journal
  • Refereed, CHEMISTRY-A EUROPEAN JOURNAL, WILEY-V C H VERLAG GMBH, Synthesis, structure, and dynamics of six-membered metallacoronands and metallodendrimers of iron and indium, RW Saalfrank; C Deutscher; H Maid; AM Ako; S Sperner; T Nakajima; W Bauer; F Hampel; BA Hess; NJRV Hommes; R Puchta; FW Heinemann, In the reaction of the N-substituted diethanolamines (H2L1-3) (1-3) with calcium hydride followed by addition of iron(m) or indium(m) chloride, the iron wheels [Fe6Cl6(L-1)(6)] (4) and [Fe6Cl6(L-2)(6)] (6) or indium wheels [In6Cl6(L-1)(6)] (5), [In6Cl6(L-2)(6)] (8) and [In6Cl6(L-3)(6)] (9) were formed in excellent yields. Exchange of the chloride ions of 6 by thiocyanate ions afforded [Fe-6(SCN)(6)(L-2)(6)] (7). Whereas the structures of 4, 5 and 7 were determined unequivocally by single-crystal X-ray analyses, complexes 8 and 9 were characterised by NMR spectroscopy. Contrary to what is normally presumed, the scaffolds of six-membered metallic wheels are not generally rigid, but rather undergo nondissociative topomerisation processes. This was shown by variable temperature (VT) H-1 NMR spectroscopy for the indium wheel [In6Cl6(L-1)(6)] (5) and is highlighted for the enantiotopomerisation of one indium centre {1/6[S-6-5] reversible arrow 1/6[S-6-5']}. The self-assembly of metallic wheels, starting from diethanolamine dendrons, is an efficient strategy for the convergent synthesis of metallodendrimers., Apr. 2004, 10, 8, 1899, 1905, Scientific journal
  • Refereed, POLYHEDRON, PERGAMON-ELSEVIER SCIENCE LTD, Self-assembly and crystal hetero-octametallic molecular box structure of a novel (Chelate complexes, Part 23), RW Saalfrank; Bernt, I; F Hampel; A Scheurer; T Nakajima; SHZ Huma; FW Heinemann; M Schmidtmann; A Muller, Reaction of hexadentate ligand m-xylene-bis-(iminodiethanol) H4L2 (4) with lithium hydride and either copper(II) acetate or copper(II) chloride resulted in the formation of two completely different products. Starting from copper(II) acetate the green bis-dimetallic cyclophane [Cu-4(H2L22)(OAc)(4)](.)2CH(2)Cl(2) (5) was formed. However, when 4 was allowed to react with copper(II) chloride, the novel hetero-octametallic molecular box {[Li-4(Cu4O)(L-2)(2)](H2O)(2)(EtOH)(2)}Cl-2 (6) was isolated. Deep violet 6 can be described as two metallacrown ether sub-units linked together by a central mu(4)-bridging O-2(-)-ion. The structures of all new compounds were determined unequivocally by single crystal X-ray analyses. (C) 2003 Elsevier Ltd. All rights reserved., Oct. 2003, 22, 22, 2985, 2989, Scientific journal
  • Refereed, JOURNAL OF PHYSICAL CHEMISTRY B, AMER CHEMICAL SOC, Nitric oxide reduction by carbon monoxide over supported hexaruthenium cluster catalysts. 1. The active site structure that depends on supporting metal oxide and catalytic reaction conditions, T Minato; Y Izumi; K Aika; A Ishiguro; T Nakajima; Y Wakatsuki, Ruthenium site structures supported on metal oxide surfaces were designed by reacting organometallic Ru cluster [Ru6C(CO)(16)](2-) or [Ru-6(CO)(18)](2-) with various metal oxides,TiO2, Al2O3, MgO, andSiO(2). The surface Ru site structure, formed under various catalyst preparation and reaction conditions, was investigated by the Ru K-edge extended X-ray absorption fine structure (EXAFS). Samples of [RU6C(CO)(16)](2-)/TiO2(anatase) and [RU6C(CO)(16)](2-)/TiO2(rutile) were found to retain the original RU6C framework when heated in the presence of NO (2.0 kPa) or NO (2.0 kPa) + CO (2.0 kPa) at 423 K, i.e., catalytic reaction conditions for NO decomposition. At 523 K, the Ru-Ru bonds of the RU6C framework were cleaved by the attack of NO. In contrast, the Ru site became spontaneously dispersed over TiO2 (anatase). When being supported over TiO2 (mesoporous), MgO, or Al2O3, the Ru6C framework split into fragments in gaseous NO or NO + CO even at 423 K. The Ru-6 framework of [RU6(CO)(18)](2-) was found to break easily into smaller ensembles in the presence of NO and/or CO at 423 K on support. Taking into consideration the realistic environments in which these catalysts will be used, we also examined the effect of water and oxygen. When water was introduced to the sample [RU6C(CO)(16)](2-)/TiO2(anatase) at 423 K, it did not have any effects on the stabilized RU6C framework structure. In the presence of oxygen gas, however, the Ru hexanclear structure decomposed into isolated Ru cations bound to surface oxygen atoms of TiO2 (anatase)., Aug. 2003, 107, 34, 9022, 9028, Scientific journal
  • Not Refereed, Photon Factory Activity Report 2001, Structural Study of the Effects of Water and Oxygen on the Nitric Oxide Decomposition on [Ru6C]/TiO2 Catalysts, Taketoshi Minato; Yasuo Izumi; Ken-ichi Aika; Atsushi Ishiguro; Takayuki Nakajima; Yasuo Wakatsuki, 2003, 19B, 18, 18
  • Refereed, CHEMISTRY-A EUROPEAN JOURNAL, WILEY-V C H VERLAG GMBH, Nanoparticles of amorphous ruthenium sulfide easily obtainable from a TiO2-supported hexanuclear cluster complex [Ru6C(CO)(16)](2-): A highly active catalyst for the reduction of SO2 with H-2, A Ishiguro; T Nakajima; T Iwata; M Fujita; T Minato; F Kiyotaki; Y Izumi; K Aika; M Uchida; K Kimoto; Y Matsui; Y Wakatsuki, TiO2-supported ruthenium-metal particles were derived from an anionic hexanuclear carbido carbonyl cluster [Ru6C(CO)(16)](2-) and compared with those prepared conventionally by impregnation of TiO2 with a solution of RuCl3 followed by reduction with H-2. The average sizes of the metal particles in both systems are similar, that is, 12 Angstrom for molecular cluster-derived particles and 15 Angstrom for those derived from the RuCl3 precursor, although the size distribution is sharper in the former case. These supported particles efficiently promote the reduction of SO2 with H-2 to give elemental sulfur. Their active form is ruthenium sulfide as confirmed by EXAFS and X-ray diffraction measurements. The nanoscale ruthenium sulfide particles, which originated from the cluster complex, have an amorphous character and show activity even at low temperature (463 K), whereas ruthenium sulfide formed from RuCl3-derived metal dispersion is a pyrite-type RuS2 crystallite and needs a temperature above 513 K to effect the same catalysis. Amorphous ruthenium sulfide maintains its nano-sized scale (approximate to 14 Angstrom) regardless of the reaction temperature, while RuS2 crystallite aggregates to form larger nonuniform particles., Jul. 2002, 8, 14, 3260, 3268, Scientific journal
  • Refereed, JOURNAL OF CATALYSIS, ACADEMIC PRESS INC ELSEVIER SCIENCE, Efficient reduction of sulfur dioxide with hydrogen over TiO2-supported catalysts derived from ruthenium salts and ruthenium cluster complexes, A Ishiguro; Y Liu; T Nakajima; Y Wakatsuki, Catalytic reduction of SO2 to elemental sulfur was carried out over supported ruthenium catalysts that were derived not only from hexaruthenium carbonyl cluster complexes but also from RuCl3 as the precursor. The activity was largely dependent on the kind of metal oxide support used. Compared to the known systems, the TiO2-supported ruthenium catalysts operated with higher efficiency at lower temperature. Moreover, the selectivity was totally to elemental sulfur, forming no detectable amount of unfavorable H2S. H2S-free catalysis appeared to be a common feature of ruthenium catalysts regardless of the kind of precursors. The TiO2-supported catalyst derived from [N(PPh3)(2)](2)[Ru6C(CO)(16)] was much more active within the 463-508 K temperature region than the catalyst conventionally prepared from RuCl3, while both showed similar activity at more elevated temperatures. The kind of cation in anionic cluster complexes and the presence of an interstitial atom are important factors in generating supported catalysts that operate under mild conditions. (C) 2002 Elsevier Science (USA)., Feb. 2002, 206, 1, 159, 164, Scientific journal
  • Refereed, SCIENTIFIC BASES FOR THE PREPARATION OF HETEROGENEOUS CATALYSTS, ELSEVIER SCIENCE BV, Supported ruthenium carbido-cluster catalysts for the catalytic removal of nitrogen monoxide and sulfur dioxide: the preparation process monitored by sulfur K-edge X-ray absorption near-edge structure, Y Izumi; T Minato; K Aika; A Ishiguro; T Nakajima; Y Wakatsuki, The preparation process of ruthenium carbido-cluster catalysts for the reduction of sulfur dioxide was traced by means of sulfur K-edge X-ray absorption near-edge structure (XANES). During the activation process, a pair of peaks at 2472.5 - 2472.8 and 2482.7 - 2482.8 eV appeared. The pair was ascribed to the M, phase. Once the catalysts were activated at 503 - 573 K, another pair of peaks at 2474.2 and 2479.2 eV appeared. The pair was assigned to the pi* and sigma* transition peaks, respectively, of adsorbed SO2 molecules on the catalyst surface., 2002, 143, 361, 368, Scientific journal
  • Refereed, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, WILEY-V C H VERLAG GMBH, Formation of super wires of clusters by self assembly of transition metal cluster anions with metal cations, T Nakajima; A Ishiguro; Y Wakatsuki, 2001, 40, 6, 1066, +, Scientific journal
  • Refereed, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, WILEY-V C H VERLAG GMBH, Synthesis of mixed-metal high-nuclearity clusters by fusion of anionic ruthenium carbido clusters through palladium units, T Nakajima; A Ishiguro; Y Wakatsuki, 2000, 39, 6, 1131, +, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, Synthesis of triangular and tetrahedral heteronuclear metal clusters using hydride complexes of cyclopentadienylrhodium and -ruthenium as the precursors, T Nakajima; Shimizu, I; K Kobayashi; Y Wakatsuki, Photochemical and/or thermal reactions of Cp*Rh(H)(2)(SiEt3)(2) (Cp* = eta(5)-C5Me5) with the dimeric metal complexes [CpNi(CO)](2) (Cp = eta(5)-C5H5), [CpCo(NO)](2), [CpRu(CO)(2)](2), and [CpFe(CO)(2)](2) yielded the trinuclear complexes (Cp*Rh)(CpNi)(2)(CO)(2) (3), (Cp*Rh)(CpCo)(2)(NO)(2) (4), (Cp*Rh)(CpM)(2)(CO)(4) (5a, M = Ru; 5b, M = Fe), respectively, while the reaction with [CpMo(CO)(2)](2) gave the tetranuclear unsaturated complex (Cp*Rh)2(CpMo)2(CO)4 (6) in good to moderate yields, Similarly, [Cp*Ru](2)(mu-H)(4) reacted with [CpNi(CO)](2), CpCo(CO)(2), and [CpFe(CO)(2)](2) to give tetrahedral (Cp*Ru)(2)(CpNi)(2)(CO)(2) (7), triangular (Cp*Ru)(2)(CpCo)(CO)(4) (8), and tetrahedral (Cp*Ru)(2)(CpFe)(2)(CO)(4) (9) complexes, respectively. The mixed-metal clusters 3, 4, 5a, and 6-9 have been structurally characterized by single-crystal X-ray diffraction., Jan. 1998, 17, 2, 262, 269, Scientific journal
  • Refereed, INORGANIC CHEMISTRY, AMER CHEMICAL SOC, Facile P-C bond cleavage of trimethylphosphine at a heterodimetallic (Ni-W) center, T Nakajima; Shimizu, I; K Kobayashi; H Koshino; Y Wakatsuki, Dec. 1997, 36, 27, 6440, 6442, Scientific journal
  • Refereed, SYNLETT, GEORG THIEME VERLAG, Facile synthesis of keto nitriles by Cu(II)-promoted photooxidative cleavage of cyclic olefins, Shimizu, I; M Fujita; T Nakajima; T Sato, Reaction of trisubstituted cyclic olefins with NaN3 in the presence of Cu(OTf)(2) upon irradiation under oxygen gave keto nitriles in good yields. 1,5-Dimethyl-1,5-cyclooctadiene and 1,5,9-trimethyl-1,5,9-cyclododecatriene were converted into the corresponding unsaturated keto nitriles., Aug. 1997, 8, 887, &, Scientific journal
  • Refereed, CHEMISTRY LETTERS, CHEMICAL SOC JAPAN, Molybdenum-catalyzed aromatic substitution with olefins and alcohols, Shimizu, I; KM Khien; M Nagatomo; T Nakajima; A Yamamoto, A new type of electrophilic aromatic substitution without using organic halides has been realized by using Mo(CO)(6) catalyst., 1997, 26, 9, 851, 852, Scientific journal
  • Refereed, ORGANOMETALLICS, AMER CHEMICAL SOC, A PHOTOCHEMICAL ROUTE TO HETEROMETALLIC COMPLEXES - SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF DINUCLEAR AND TRINUCLEAR COMPLEXES HAVING A MOLYBDENOEENE OR TUNGSTENOCENE UNIT, T NAKAJIMA; T MISE; SHIMIZU, I; Y WAKATSUKI, Irradiation of a mixture of tungstenocene or molybdenocene dihydride and a metal-metal-bonded dimeric complex has been found to be a convenient route to homo- and heterometallic complexes. The photoreactions of (eta(5)-C5H5)(2)M(1)H(2) With [(eta(5)-C5H5)M(2)(CO)(3)](2) (M(1), M(2) = W, Mo) in DME afford in good yields the bimetallic complexes (eta(5)-C5H5)(CO)M(1)(mu,sigma-eta(5)-C5H4)-M(2)(CO)(2)(eta(5)-C5H5) with a M(1)-M(2) bond. (1a, M(1) = W, M(2) = Mo; 1b, M(1) = Mo, M(2) = W; 1C, M(1) = M(2) = W; 1d, M(1) = M(2) = MO). BY use of [(eta(5)-C(5)R(5))Ni(CO)](2) as the dimer part, the heterobimetallic hydrides (eta(5)-C5H5)(2)M(mu-H)(mu-CO)Ni(C(5)R(5)) (2a, M = W, R = H; 2b, M = W, R = Me; 2c, M = Mo, R = H, 2d, M = Mo, R = Me) were obtained, where the two metallocene cyclopentadienyl rings remain intact and the metal-metal bond is bridged by CO and hydride. Similar photolysis of a mixture of (eta(5)-C5H5)(2)MH(2) and [(eta(5)-C5H5)Ru(CO)(2)](2) has afforded two trimetallic complexes: (eta(5)-C5H5)(mu,sigma-eta(5)-C5H4)M(mu-CO)(2)Ru(eta(5)-C5H5)Ru(eta(5)-C5H5)-(CO)H (3a, M = W; 3b, M = Mo), where the Ru-Ru bond still exists with a new M-Ru bond and one bridging (mu,sigma-eta(5)-C5H4) ring between M and the other Ru, and (mu,sigma-eta(5)-C5H4)(2)-Mh(2)[(eta(5)-C5H5)Ru(CO)](2) (4a, M = W; 4b, M = Mo), in which both of the cyclopentadienyl rings of the metallocene are metalated with Ru. The crystal and molecular structures of 1a, 2d, 3a, and 4a have been determined by single-crystal X-ray diffraction analysis., Dec. 1995, 14, 12, 5598, 5604, Scientific journal
  • Refereed, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER SCIENCE SA LAUSANNE, PREPARATION AND STRUCTURE OF THE 1ST ANSA-MOLYBDENOCENE AND TUNGSTENOCENE DERIVATIVES - REACTION OF [O(SIME2C5H4)2]MOH2 WITH METHYL-METHACRYLATE TO PROBE THE OLEFIN ATTACKING SITE, T MISE; M MAEDA; T NAKAJIMA; K KOBAYASHI; SHIMIZU, I; Y YAMAMOTO; Y WAKATSUKI, Bridged-bis(cyclopentadienyl) molybdenum and tungsten dihydrides and their derivatives have been synthesized for the first time. [(1,1,3,3-Tetramethyldisiloxane-1,3-diyl)bis(eta5-cyclopentadienyl)]molybdenum dihydride (1a) and tungsten dihydride (1b) were prepared by sodium borohydride reduction of [O(SiMe2C5H4)2]MCl2 (2a: M = Mo, 2b: M = W) which was obtained by the reaction of disodium 1,1,3,3-tetramethyl-1,3-bis(cyclopentadienyl)disiloxane with MCl4(thf)2 (M = Mo, W). The dichlorides 2 reacted with ZnMe2 and NaSEt to afford [O(SiMe2C5H4)2]MMe2 (3a: M = Mo, 3b: M = W) and [O(SiMe2C5H4)2]M(SEt)2 (4a: M = Mo, 4b: M = W), respectively. Photolysis of lb in benzene gave [O(SiMe2C5H4)2]WH(C6H5) (5b). An X-ray crystal analysis of 3a has proved that the bridging chain blocks one of the side positions of the complex, the siloxy unit being present at one side of the Me-Mo-Me bisector. Consistent with side position attack by olefins, the reaction rate of la with methyl methacrylate was found to be nearly one half that of the parent CP2MoH2 (6a)., Jun. 1994, 473, 1-2, 155, 162, Scientific journal
  • Chemistry – A European Journal, Wiley, Cover Feature: Octapalladium Strings Trap C 60 and C 70 Fullerenes Affording Metal‐Chain‐Wired Bucky Balls (Chem. Eur. J. 51/2021), Tomoaki Tanase; Kanako Nakamae; Yasutaka Kitagawa; Takayuki Nakajima, 09 Sep. 2021, 27, 51, 12918, 12918, Scientific journal
  • Chemistry – A European Journal, Wiley, Cover Feature: Fine Tunable, Redox Active Octapalladium Chains Supported by Linear Tetraphosphines, Leading to Dynamically 1D Self‐Assembled Coordination Polymers (Chem. Eur. J. 47/2021), Tomoaki Tanase; Kanako Nakamae; Haruka Miyano; Yasuyuki Ura; Yasutaka Kitagawa; Shiho Yada; Tomokazu Yoshimura; Takayuki Nakajima, 19 Aug. 2021, 27, 47, 12010, 12010, Scientific journal
  • Refereed, Coordination Chemistry Reviews, Elsevier BV, Fine tunable metal assemblies constrained by multidentate phosphine ligands, Tomoaki Tanase; Kanako Nakamae; Yasuyuki Ura; Takayuki Nakajima, Sep. 2022, 466, 214581, 214581, Scientific journal
  • Refereed, European Journal of Inorganic Chemistry, Wiley, Tetranuclear Pd 4 , Pt n Pd 4‐ n ( n =1–3), and Pt 4 Chains Supported by rac ‐ and meso ‐Ph 2 PCH 2 P(Ph)N(Ar)P(Ph)CH 2 PPh 2 Tuned by Changing N ‐Substituents, P ‐Configuration, and Terminal Ligands, Tomoaki Tanase; Yoshimi Fujisawa; Yuka Morita; Yasuyuki Ura; Takayuki Nakajima, 17 May 2022, e202200248, Scientific journal

MISC

  • Not Refereed, 教育システム研究, サイエンス・オープンラボを通した化学(電池の歴史、化学発光)学習ー大学生による演示実験を動機付けにした高等学校授業開発研究ー, TAKASHIMA Hiroshi; TAKEUCHI Takae; MIKATA Yuji; URA Yasuyuki; NAKAJIMA Takayuki; MATSUURA Noriyuki, Mar. 2019, 14, 103, 111
  • Not Refereed, 觸媒 = Catalyst, 触媒学会, 固定化ルテニウムクラスター触媒の調製とNO還元反応, 湊 丈俊; 泉 康雄; 秋鹿 研一; 吉武 英昭; 石黒 淳; 中島 隆行; 若槻 康雄, 10 Mar. 2002, 44, 2, 95, 97
  • Not Refereed, Photon Factory Activity Report 2000, Sulfur K-edge XAFS Study of Supported Ruthenium Cluster Catalysts, Yasuo Izumi; Atsushi Ishiguro; Taketoshi Minato; Takayuki Nakajima; Yasuo Wakatsuki, 2002, 18B, 38, 38, Report research institution
  • Not Refereed, 触媒, 触媒学会, 担持ルテニウムクラスター触媒を用いたSO_2還元反応とXAFSによる触媒種のキャラクタリゼーション, 石黒 淳; 劉 宇; 中島 隆行; 湊 丈俊; 清瀧 史貴; 泉 康雄; 秋鹿 研一; 岩槻 康雄, 10 Sep. 2001, 43, 6, 382, 384
  • Not Refereed, RIKEN Review, High-Nuclearity Cluster Complexes and Their Reaction with Air-Polluting SO2 Gas Molecules, NAKAJIMA Takayuki; T. Nakajima; A. Ishiguro; Y. Liu; T. Chihara; Y. Wakatsuki, 2001, 42, 45, 48
  • Not Refereed, RIKEN Review, 1H-31P Pulsed Field Gradient Heteronuclear Multiple-Bond Correlation (PFG-HMBC) Spectroscopy, NAKAJIMA Takayuki; H. Koshino; T. Nakajima; Y. Wakatsuki; K. Kobayashi; J. Uzawa, 1996, 12, 37, 38

Presentations

  • 田窪瑞季; 前田侑希; 中前佳那子; 中島隆行; 棚瀬知明, 第71回錯体化学討論会, 四座ホスフィン配位子meso-dpmpppに支持されたRh(I)を含む非対称型同種・異種金属二核錯体を用いたオレフィンのヒドロシリル化反応, Oral presentation, 18 Sep. 2021, 17 Sep. 2021, 19 Sep. 2021
  • 藤澤良実; 森田優花; 田中美帆; 中前佳那子; 浦康之; 中島隆行; 棚瀬知明, 第71回錯体化学討論会, PNP架橋を含む直鎖状四座ホスフィンに支持された直鎖状Pd4核錯体における四座配位子N-置換基及び軸配位子の効果, 17 Sep. 2021, 17 Sep. 2021, 19 Sep. 2021
  • 森田優花; 藤澤良実; 中前佳那子; 中島隆行; 棚瀬知明, 日本化学会第100回春季年会, Synthesis of Mixed-Metal Pd/Pt Tetranuclear Complexes Supported by Tetraphosphine Ligands, Oral presentation, 24 Mar. 2020, 22 Mar. 2020, 25 Mar. 2020
  • 前田侑希; 中前佳那子; 中島隆行; 棚瀬知明, 日本化学会第100回春季年会, Synthesis of Unsymmetric Dinuclear Iridium Complexes Supported by Tetraphosphine Ligands and Their Reactivity, Oral presentation, 23 Mar. 2020, 22 Mar. 2020, 25 Mar. 2020
  • 田窪瑞季; 今井香歩; 中前佳那子; 中島隆行; 棚瀬知明, 日本化学会第100回春季年会, Synthesis of MCu Heterometallic Dinuclear Complexes (M = Ni, Pd, Pt) Supported by a Tetraphosphine Ligand and Their Reactions, Oral presentation, 22 Mar. 2020, 22 Mar. 2020, 25 Mar. 2020
  • 前田侑希; 中前佳那子; 中島隆行; 棚瀬知明, 第69回錯体化学討論会, Synthesis and Reactions of Unsymmetric Dinuclear Rhodium Complexes Supported by a Tetraphosphine Ligand Containing an Amino Group, Oral presentation, 23 Sep. 2019, 21 Sep. 2019, 23 Sep. 2019
  • 森田優花; 田中美帆; 濱田磨美; 中前佳那子; 浦康之; 中島隆行; 棚瀬知明, 第69回錯体化学討論会, Synthesis and Reactivity of Pd/Pt Mixed-Metal Tetranuclear Chains Supported by a New Linear Tetraphosphine Containing a PNP bridge, Oral presentation, 21 Sep. 2019, 23 Sep. 2019
  • 今井香歩; 中前佳那子; 浦康之; 中島隆行; 棚瀬知明, 第66回有機金属化学討論会, Reaction Mechanism of Formic Acid Dehydrogenation Catalyzed by Unsymmetric Dinuclear Copper Complexes, 16 Sep. 2019, 14 Sep. 2019, 16 Sep. 2019
  • Kanako Nakamae; Takayuki Nakajima; Tomoaki Tanase, The 99th CSJ Annual Meeting, Chiral Octapalladium Chains, 17 Mar. 2019, False
  • Miho Tanaka; Kanako Nakamae; Yasuyuki Ura; Takayuki Nakajima; Tomoaki Tanase, The 99th CSJ Annual Meeting, Linear Mixed-Metal Pd4-nPtn (n = 0—3) Tetranuclear Complexes Supported by Imino-bridged Tetraphosphines, rac-dpmppan, 17 Mar. 2019, False
  • Kanako Nakamae; Takayuki Nakajima; Tomoaki Tanase, The 99th CSJ Annual Meeting, Hydrogenation of CO2 Catalyzed by Dinuclear Copper Hydride Complexes, 16 Mar. 2019, False
  • 前田侑希; 中前佳那子; 中島隆行; 棚瀬知明, 日本化学会第99回春季年会, アミノ基を有する新奇四座ホスフィン配位子に支持されたRh二核錯体の合成とHClとの反応性, 16 Mar. 2019, False
  • Takayuki Nakajima; Yoshia Kamiryo; Kanae Hachiken; Kanako Nakamae; Yasuyuki Ura; Tomoaki Tanase, The 43st International Conference on Coordination Chemistry (ICCC2018), Tri- and Tetranuclear Copper Hydride Complexes Supported by Tetradentate Phosphine Ligands, 04 Aug. 2018, False
  • Miho Tanaka; Kanako Nakamae; Yasuyuki Ura; Bunsho Kure; Takayuki Nakajima; Tomoaki Tanase, The 43st International Conference on Coordination Chemistry (ICCC2018), A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and Its Facile Reaction with CO2, 01 Aug. 2018, True
  • 日本化学会第98回春季年会, アミノ基を有する新奇直鎖状四座ホスフィン rac-dpmppan に支持されたパラジウム4核錯体の合成, 2018
  • 日本化学会第98回春季年会, 直鎖状四座ホスフィンmeso-dpmppmに支持されたAフレーム型白金3核錯体の合成と反応, 2018
  • 日本化学会第98回春季年会, 四座ホスフィン配位子meso-dpmpppで支持されたロジウム二核錯体のアミン類による還元的脱塩素化反応, 2018
  • 日本化学会第97回春季年会, 四座ホスフィン配位子とジイミン系配位子に支持された銅(I)二核錯体の合成と発光特性, 2017
  • 日本化学会第97回春季年会, 三座ホスフィンにより支持された直鎖状白金三核テトラヒドリド錯体の合成と構造, 2017
  • 日本化学会第97回春季年会, 四座ホスフィンmeso-dpmppmを配位とするイリジウム単核ヒドリド錯体の合成と反応性, 2017
  • 日本化学会第97回春季年会, 直鎖状四座ホスフィンrac-dpmppeに支持された銅(Ⅰ)四核ヒドリド錯体の合成, 2017
  • 日本化学会第97回春季年会, 二座ホスフィンに支持された銅ヒドリド 8 核錯体の動的挙動と CO2 及び CO との反応, 2017
  • International Symposium on Pure & Applied Chemistry 2017 (ISPAC2017), Synthesis and Reactivity of Dinuclear Complexes Supported by Tetradentate Phosphine Ligands, 2017
  • 第67回錯体化学討論会, Pd4核ユニット間の不斉自己認識によるホモキラルな四座ホスフィンに支持された直鎖状Pd8核錯体の生成, 2017
  • 第67回錯体化学討論会, 銅 8 核ヒドリド錯体を用いた二酸化炭素のヒドロシリル化を 伴うジシロキサン生成反応, 2017
  • 第67回錯体化学討論会, 四座ホスフィンに支持された銅(I)二核及び四核イソシアニド錯体の合成と構造及び平衡反応, 2017
  • 第67回錯体化学討論会, 分岐型ホスフィン配位子に支持された銅(I)及び金(I)多核錯体の合成と性質, 2017
  • 第67回錯体化学討論会, 四座ホスフィン配位子とジイミン系配位子に支持された銅(I)二核錯体の合成と発光特性, 2017
  • 第67回錯体化学討論会, 四座ホスフィンmeso-dpmppmを用いたピンサー型白金単核錯体の合成と反応性, 2017
  • 4th Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry, A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and Its Facile Reaction with CO2, 2017
  • International Symposium on Pure & Applied Chemistry 2017 (ISPAC2017), Synthesis and Reactivity of Dinuclear Complexes Supported by Tetradentate Phosphine Ligands, 2017
  • 4th Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry, A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and Its Facile Reaction with CO2, 2017
  • 日本化学会第95回春季年会, Syntheses and Structures of Copper Hydride Clusters Supported by Multidentate Phosphine Ligands, 2016
  • 日本化学会第95回春季年会, ビスイソシアニドで連結した直鎖状パラジウム八核錯体ポリマーの合成と性質, 2016
  • 日本化学会第95回春季年会, Activation of Hydrosilanes by Novel Dithilate-Bridged NiIr Dinuclear Complexes Supported by a P2S2 Tetradentate Ligand, 2016
  • 日本化学会第95回春季年会, 四座ホスフィン dpmppp に支持された非対称イリジウム(I)二核中心におけるオルトメタル化反応, 2016
  • 日本化学会第95回春季年会, 分岐型四座ホスフィンに支持されたイソシアニドを末端配位子とする直鎖状白金三核錯体の合成と性質, 2016
  • 日本化学会第95回春季年会, 四座ホスフィン配位子を用いたロジウム(I)四核錯体の小分子との反応, 2016
  • 日本化学会第95回春季年会, 四座ホスフィンdpmppeを支持配位子としたイリジウム二核錯体の合成と反応性, 2016
  • 日本化学会第95回春季年会, キラルな四座ホスフィン配位子 rac-dpmppm により支持された直鎖状パラジウム八核錯体の酸化還元挙動, 2016
  • 日本化学会第95回春季年会, 四座ホスフィンに支持された銅(Ⅰ)三核及び四核ヒドリド錯体の合成と反応性, 2016
  • 日本化学会第95回春季年会, 六座ホスフィン配位子に支持されたAu(I) 7核錯体の合成と構造, 2016
  • 27th International Conference on Organometallic Chemistry, Systematic Synthesis of Heterodinuclear Complexes with NiM(m-SR)2 (M = Rh, Ir) and Their Reactivity toward Organic Substrates, 2016
  • 第66回錯体化学討論会, 四座ホスフィン配位子rac-dpmppmによって三重架橋された後周期遷移金属二核錯体の合成と性質, 2016
  • 第66回錯体化学討論会, キラルな四座ホスフィン配位子 rac-dpmppm により支持された直鎖状パラジウム八核錯体の酸化還元挙動, 2016
  • 第66回錯体化学討論会, 四座ホスフィンに支持された銅(Ⅰ)三核及び四核ヒドリド錯体, 2016
  • 第66回錯体化学討論会, 分岐型ホスフィン配位子に支持された平面状白金多核錯体の合成と性質, 2016
  • 第63回有機金属化学討論会, 多座ホスフィンで支持した銅ヒドリドクラスターの合成と二酸化炭素との反応, 2016
  • 第63回有機金属化学討論会, 四座ホスフィン配位子rac-dpmppmによって三重架橋された後周期遷移金属二核錯体の合成と性質, 2016
  • The 96th CSJ Annual Meeting, Syntheses and Structures of Copper Hydride Clusters Supported by Multidentate Phosphine Ligands, 2016
  • The 96th CSJ Annual Meeting, Activation of Hydrosilanes by Novel Dithilate-Bridged NiIr Dinuclear Complexes Supported by a P2S2 Tetradentate Ligand, 2016
  • 27th International Conference on Organometallic Chemistry, Systematic Synthesis of Heterodinuclear Complexes with NiM(m-SR)2 (M = Rh, Ir) and Their Reactivity toward Organic Substrates, 2016
  • 日本化学会第95回春季年会, 分岐型四座ホスフィンで支持された直鎖状白金三核錯体の合成, 2015
  • 日本化学会第95回春季年会, イソシアニドを軸配位子とする直鎖状パラジウム四核錯体の合成と性質, 2015
  • 日本化学会第95回春季年会, 四座ホスフィンを用いた多核銅(I)ヒドリド錯体の合成と反応性, 2015
  • 日本化学会第95回春季年会, P2S2型四座配位子を有するNiIIRhIおよびNiIIIrI二核錯体の合成と構造及び反応性, 2015
  • 日本化学会第95回春季年会, キラルな四座ホスフィン配位子 rac-dpmppm により支持された直鎖状パラジウム八核錯体の合成と性質, 2015
  • 日本化学会第95回春季年会, 四座ホスフィン配位子によって支持された電子不足なロジウム二核中心への HCl の酸化的付加, 2015
  • 日本化学会第95回春季年会, 長鎖アルキル基を有するイソシアニドが軸配位した直鎖状パラジウム八核錯体の合成と性質, 2015
  • 第65回錯体化学討論会, ハロゲン末端配位子とキラルな四座ホスフィンで支持した直鎖状パラジウム八核錯体の合成と構造, 2015
  • 第65回錯体化学討論会, 四座ホスフィンで支持した銅9 核および銅16 核ヒドリドクラスターの構造と電子状態, 2015
  • 第65回錯体化学討論会, 四座ホスフィン配位子dpmppp によって支持された電子不足なロジウム二核中心へのHCl の酸化的付加, 2015
  • 第65回錯体化学討論会, ビスイソシアニドまたは長鎖アルキルイソシアニドが配位した直鎖状パラジウム八核錯体の合成と性質, 2015
  • The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem), Redox Properties of Linear Octanuclear Palladium Complexes Supported by Tetraphosphine Ligands, 2015
  • The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem), A Linear Hexanuclear Platinum Trihydride Complex Supported by Triphosphine Ligands, 2015
  • The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem), Redox Properties of Linear Octanuclear Palladium Complexes Supported by Tetraphosphine Ligands, 2015
  • The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem), A Linear Hexanuclear Platinum Trihydride Complex Supported by Triphosphine Ligands, 2015
  • 日本化学会第94回春季年会, 四座ホスフィン配位子 dpmppm によって支持された直鎖状 Pt2Ag2 異種金属四核錯体の合成と発光特性, 2014
  • 日本化学会第94回春季年会, 四座ホスフィン配位子によって支持されたロジウム二核錯体の HCl に対する反応性, 2014
  • 日本化学会第94回春季年会, ジチオラト架橋を有する異種金属二核錯体の合成および構造, 2014
  • 日本化学会第94回春季年会, 直鎖型六座ホスフィン配位子に支持された直鎖状Ag(I)六核錯体およびAg(I)Pt(II)六核錯体の合成と構造, 2014
  • 日本化学会第94回春季年会, ビスカルボキシラト配位子に支持されたマンガン二核錯体の合成および構造と反応性, 2014
  • 日本化学会第94回春季年会, 新規四座ホスフィンスルフィド配位子を用いた銅錯体の合成と構造, 2014
  • 日本化学会第94回春季年会, 直鎖状パラジウム八核錯体と酸との反応, 2014
  • the XXVI International Conference on Organometallic Chemistry (ICOMC 2014), Reversible Dioxygen Binding on Asymmetric Dinuclear Rhodium Centers, 2014
  • the XXVI International Conference on Organometallic Chemistry (ICOMC 2014), Reduction of Carbon Dioxide with Copper Hydride Complexes Supported by Tetraphosphine, 2014
  • the XXVI International Conference on Organometallic Chemistry (ICOMC 2014), Heterodinuclear Complexes with MM’(m-meppp) Cores (M = Ni, Pd, Pt; M’ = Rh, Ir) That Tune Property of a Nesting Hydride, 2014
  • The 41st International Conference on Coordination Chemistry (ICCC41), Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of NiII, CoII, and CuII Ions Supported by Unsymmetrical Aminoalcohol Ligands, 2014
  • The 41st International Conference on Coordination Chemistry (ICCC41), Cage-Type Copper Hydride Clusters Supported By Tetraphosphine Ligands, 2014
  • 第64回錯体化学討論会, 四座ホスフィンで支持した直鎖状パラジウム八核錯体の酸化還元挙動, 2014
  • 第64回錯体化学討論会, 多座ホスフィン配位子に支持された同種および異種金属Ag多核錯体の合成と構造・性質, 2014
  • 第64回錯体化学討論会, ビスカルボキシラト架橋マンガン二核錯体の合成と糖リン酸エステルとの反応, 2014
  • 第64回錯体化学討論会, 三座ホスフィンで支持された直鎖白金多核錯体の集積, 2014
  • 第61回有機金属化学討論会, 銅2核及び4核ヒドリド錯体を用いた二酸化炭素の還元反応, 2014
  • the XXVI International Conference on Organometallic Chemistry (ICOMC 2014), Reversible Dioxygen Binding on Asymmetric Dinuclear Rhodium Centers, 2014
  • the XXVI International Conference on Organometallic Chemistry (ICOMC 2014), Reduction of Carbon Dioxide with Copper Hydride Complexes Supported by Tetraphosphine, 2014
  • the XXVI International Conference on Organometallic Chemistry (ICOMC 2014), Heterodinuclear Complexes with MM’(m-meppp) Cores (M = Ni, Pd, Pt; M’ = Rh, Ir) That Tune Property of a Nesting Hydride, 2014
  • The 41st International Conference on Coordination Chemistry (ICCC41), Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of NiII, CoII, and CuII Ions Supported by Unsymmetrical Aminoalcohol Ligands, 2014
  • The 41st International Conference on Coordination Chemistry (ICCC41), Cage-Type Copper Hydride Clusters Supported By Tetraphosphine Ligands, 2014
  • 日本化学会第93回春季年会, アニオン性軸配位子を有する直鎖状パラジウム八核錯体の合成と構造, 2013
  • 日本化学会第93回春季年会, 四座ホスフィン配位子により構造規制された直鎖状金(I)四核錯体の異性体構造と発光挙動, 2013
  • 日本化学会第93回春季年会, 電子求引性置換基を有する四座ホスフィン配位子により支持された直鎖状パラジウム四核錯体, 2013
  • 第60回有機金属化学討論会, 四座ホスフィンで構造規制した低原子価直鎖状パラジウム八核錯体, 2013
  • 第63回錯体化学討論会, 四座ホスフィン配位子 rac-dpmppm に支持された後周期遷移金属二核錯体の合成と性質, 2013
  • 第63回錯体化学討論会, 四座ホスフィン dpmppp を支持配位子としたイリジウム二核錯体の合成及び構造, 2013
  • 第63回錯体化学討論会, S2P2型四座配位子を有するジチオラト架橋NiRh二核錯体の反応性, 2013
  • 第63回錯体化学討論会, 四座ホスフィンdpmppmで支持した銅(I)ヒドリド錯体を用いた二酸化炭素の還元反応, 2013
  • 第63回錯体化学討論会, 長鎖アルキル基を有するイソシアニド配位子を用いた直鎖状白金三核及び六核錯体の合成と性質, 2013
  • 第63回錯体化学討論会, 新規直鎖型六座ホスフィン配位子に支持された金(Ⅰ)六核錯体の合成と構造および発光特性, 2013
  • 第63回錯体化学討論会, 電子吸引性置換基を有する四座ホスフィン配位子に支持された直鎖状パラジウム四核錯体の合成と性質, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Reduction of Carbon Dioxide with Copper Hydride Complexes Supported by Tetraphosphine, dpmppm, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Strongly Luminous, Linear Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Reversible Dioxygen Binding on Asymmetric Dinuclear Rhodium Centers Supported by a Tetraphosphine, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Dithiolate-bridged Heterodinuclear Complexes, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Linearly Ordered Tri- and Hexanuclear Platinum Complexes, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Synthesis and Characterization of Linear Tetranuclear Palladium Complexes Supported by Tetraphosphine, 2013
  • International Symposium on Catalysis and Fine Chemicals 2013, Reversible dioxygen binding on asymmetric dinuclear rhodium centers, 2013
  • International Symposium on Catalysis and Fine Chemicals 2013, Reduction of Carbon Dioxide with Copper Hydride Complexes Supported by Tetraphosphine Ligand, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Reduction of Carbon Dioxide with Copper Hydride Complexes Supported by Tetraphosphine, dpmppm, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Strongly Luminous, Linear Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Reversible Dioxygen Binding on Asymmetric Dinuclear Rhodium Centers Supported by a Tetraphosphine, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Dithiolate-bridged Heterodinuclear Complexes, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Linearly Ordered Tri- and Hexanuclear Platinum Complexes, 2013
  • The 2nd Japan-France Coordination Chemistry Symposium 2013, Synthesis and Characterization of Linear Tetranuclear Palladium Complexes Supported by Tetraphosphine, 2013
  • International Symposium on Catalysis and Fine Chemicals 2013, Reversible dioxygen binding on asymmetric dinuclear rhodium centers, 2013
  • International Symposium on Catalysis and Fine Chemicals 2013, Reduction of Carbon Dioxide with Copper Hydride Complexes Supported by Tetraphosphine Ligand, 2013
  • XXV International Conference on Organometallic Chemistry, Multinucleation of Late Transition Metals with New Tetraphosphine Ligands, 2012
  • XXV International Conference on Organometallic Chemistry, Linear Octanuclear Palladium Complexes with Axial Nitrile Ligands, 2012
  • 第59回有機金属化学討論会, N3S2型ジチオラト配位子によって架橋されたNiRh, 2012
  • 第59回有機金属化学討論会, NPPN型四座位配位子を用いたIr, Rh二核錯体の異性化反応, 2012
  • 第62回錯体化学討論会, 四座ホスフィン dpmppp を支持配位子としたロジウム二核錯体の合成と酸素分子との反応, 2012
  • 第62回錯体化学討論会, フェロセニル基を有するイソシアニド軸配位子を用いた直鎖状白金三核及び六核錯体の合成と性質, 2012
  • 第62回錯体化学討論会, S2P2型四座配位子によって支持されたチオラト架橋異種金属ヒドリド二核錯体の合成と反応性, 2012
  • 第62回錯体化学討論会, 四座ホスフィン meso-dpmppm を用いた溶媒分子を軸配位子とする直鎖状パラジウム八核錯体, 2012
  • 第62回錯体化学討論会, 四座ホスフィン配位子 rac-dpmppm により支持された直鎖状パラジウム八核錯体の合成と性質, 2012
  • The Japanese-German Symposium on Coordination Programming, Polynuclear Copper Hydride Complexes, 2012
  • XXV International Conference on Organometallic Chemistry, Multinucleation of Late Transition Metals with New Tetraphosphine Ligands, 2012
  • XXV International Conference on Organometallic Chemistry, Linear Octanuclear Palladium Complexes with Axial Nitrile Ligands, 2012
  • The Japanese-German Symposium on Coordination Programming, Polynuclear Copper Hydride Complexes, 2012

Industrial Property Rights

  • Patent right, 13C標識ベンゼンの製造方法及び13C標識ベンゼン誘導体, 清水 功雄, 関根 泰, 中島 隆行, 木下 純一, 栗下 晴人, 小林 祥一朗, 清水 勇佑, 新関 一馬, 小西 康雄, 宮里 典江, 東京ガスケミカル株式会社 , 学校法人早稲田大学, 特願2007-107901, 17 Apr. 2007
  • Patent right, 硫黄酸化物の還元用触媒, 石黒 淳, 中島 隆行, 若槻 康雄, 理化学研究所, 特願2001-044933, 21 Feb. 2001
  • Patent right, オレフィンの重合方法, 三瀬 孝也, アルノ フリース, 中島 隆行, 大森 弘亨, 松本 昭, 山本 澄雄, 池上 祐司, 若槻 康雄, 独立行政法人理化学研究所, 特願平8-045903, 04 Mar. 1996

Research Projects

  • Grant-in-Aid for Scientific Research (A), Apr. 2018, Mar. 2023, 18H03914, Coinvestigator, New Materials Fabricated by Nano-Scale Dimensional Integration of Finely Constructed Multinuclear Metal Systems, 棚瀬 知明; 中島 隆行; 浦 康之; 中前 佳那子, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (A), Nara Women's University, 43030000, 33100000, 9930000, (1)直鎖状及び分枝状多座ホスフィン配位子の合成: N原子で連結された直鎖状四座ホスフィン(dpmppaR, R = Ph,Tol等)を合成し,ホモキラルなdpmppaPhにより支持された直鎖状Pd4核鎖及び一連のPd/Pt混合金属4核鎖(PtPd3, PtPd2Pt, Pt2Pd2, Pt2PdPt)を構築することで一次元合金金属鎖という新たな概念の分子素子を開発し論文発表した(Chem. Eur. J. 2019)。(2)低原子価Pd, Pt分子ワイヤーの創成: キラルな直鎖状四座ホスフィンdpmppmを用いたパラジウム分子ワイヤーの合成と自己不斉認識によるPd鎖の拡張として,rac-dpmppmをHPLCキラルカラムにより光学分割し,キラルなPd8核鎖を合成し単離することに成功した。また,錯体合成による光学分割手法も開発した。(3)閉殻金属を用いた環状クラスターの分子設計と光励起物性の発現:光学活性なdpmppmを用いて強い発光を示すAu(I)四核錯体の合成を行った。また,多座ホスフィンオキシドを用いることでランタニド2核錯体を合成し,円二色性スペクトルや円偏光発光について研究を進めた。(4)銅ヒドリド多核金属集合系を用いた貴金属代替材料の開発:かご状銅ヒドリド8,9,16核錯体を合成しその構造や反応性を明らかにした。特に8核錯体は二酸化炭素の水素化を触媒することが明らかとなり,強塩基存在下で触媒的なギ酸生成反応を確立した(Angew. Chem. Int. Ed. 2020)。(5)銅ヒドリド種を用いた有機触媒反応の開発:ブチレン鎖を有する直鎖状四座ホスフィンの銅ヒドリド6核錯体が,ギ酸の水素と二酸化炭素への分解反応を触媒することが明らかにし,最終的に非対称銅二核中心による高活性なギ酸分解触媒システムを開発した(J. Am. Chem. Soc. 2019)。, rm:published_papers
  • Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area), Apr. 2019, Mar. 2021, 19H04582, Principal investigator, Development of Chiral Molecular Metal Chains, 中島 隆行, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area), Nara Women's University, 4940000, 3800000, 1140000, 本新学術領域研究では,キラルな直鎖状四座ホスフィンrac-dpmppm (Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2)を用いたキラルなPd8核鎖の物性開発(研究課題①)や、dpmppmの中央のメチレン炭素を電子的・立体的に調整可能でかつキラルな置換基Rの導入も容易なイミノ基に置換した新奇な四座ホスフィンrac-Ph2PCH2P(Ph)N(R)P(Ph)CH2PPh2を用いたキラルな金属鎖に関する研究(研究課題②)を行っている。今回は研究課題②の配位子の知見を得る目的で行ったrac-dpmppan (R = Ph)による混合金属4核錯体について報告する。rac-dpmppan に [M2(XylNC)6](PF6)2 (M = Pd, Pt) 及び [Pd(dba)2] を 2:1:2 の比で反応させると,直鎖状 4 核錯体 [PtnPd(4-n)(rac-dpmppan)2(XylNC)2](PF6)2 (n = 0: Pd4 (1), 2: Pt2Pd2 (4)) が得られた。電子吸収スペクトルでは,アセトニトリル中室温で,634 (1),601 (2),584 (3),527 (4), 510 (5) nm に特徴的な吸収が観測され,吸収エネルギーは金属骨格に含まれる白金の数と位置に応じて変化することがわかった 。結晶構造をもとに TD-DFT の一点計算を行うと,強い振動子強度で HOMO-LUMO遷移由来する吸収が予想され,その計算値は観測値と概ね一致した。金属骨格(Pt/Pd)の組み合わせで HOMO-LUMO gapを精密にチューニングできることが分かり,合金ナノワイヤーを原子レベルで精密に構築する上での重要な知見につながる。今後はキラルな置換基Rを導入した配位子を用いてキラルな混合金属鎖合成へと展開する予定である。, rm:published_papers
  • Grant-in-Aid for Scientific Research (C), Apr. 2017, Mar. 2020, 17K05812, Principal investigator, Synthesis and reactivity of pincer type dinuclear complexes with metal-metal dative bond, Nakajima Takayuki, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C), Nara Women's University, 4680000, 3600000, 1080000, We have utilized four linear tetradentate phosphine ligands with longer central methylene chains and different configurations at the inner phosphorous atoms, meso- and rac-Ph2PCH2P(Ph)(CH2)nP(Ph)CH2PPh2 (n = 2: dpmppe, 3:dpmppp, 4:dpmppb) to modulate the structures and reactivity of copper hydride species. These ligands gave a series of multinuclear copper hydride complexes with a variety of metal frameworks. Among these copper hydride complexes, only the copper hydride supported by meso-dpmppb showed reactivity toward CO2. Furthermore, the copper hydride was found to be a suitable catalyst for formic acid dehydrogenation into H2 and CO2. An unsymmetric dinuclear copper motif bridged by tetradentate phosphine ligands, was proposed as an active species to promote the decomposition of FA by virtue of synergistic effects of the Cu2 unit. The present system is the first distinguished catalytic dehydrogenation of FA by using cheap base metallic Cu complexes., url
  • Grant-in-Aid for Scientific Research (B), Apr. 2014, Mar. 2017, 26288025, Coinvestigator, Development of New Functional Materials by Nano-scale Molecular Design and Expansion of Multinuclear Metal Systems, TANASE Tomoaki, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (B), Nara Women's University, 17290000, 13300000, 3990000, This project intended development of new functional materials by expanding multinuclear metal systems which are designed in fine tunable fashion as metal chains, rings, and cages, etc. with an aid of systematically synthesized linear polyphosphine ligands. In particular, rigid-rod platinum and palladium wires (Pt6, Pd8), flexible gold and silver chains (Au4, Au6, Ag6), gold-silver-copper rings (Au4Ag2Cu2), and multinuclear copper hydride complexes (Cu2, Cu4, Cu8, Cu9, Cu16) were synthesized and characterized, and their properties and reactivity as well as expansion by using metal and organic linkers were examined., url
  • Grant-in-Aid for Scientific Research (C), Apr. 2013, Mar. 2016, 25410069, Principal investigator, Synthesis and Reactivity of Dinuclear Complexes Supported by Linear Tetraphosphine Ligands, Takayuki Nakajima; Tanase Tomoaki, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C), Nara Women's University, 5200000, 4000000, 1200000, With an aim to develop new reaction promoted by cooperative effects from two proximate metal centers that would not be established by single metal center, synthesis and reactivities of dinuclear complexes supported by linear tetraphosphine dpmppp ligand were investigated. The aromatic C-H bond activation at dinuclear iridium complexes is assumed to proceed through a two-metal-cooperative pathway switching metal-to metal dative interactions on and off based on X-ray analysis and theoretical calculations., url
  • Grant-in-Aid for Scientific Research (C), 2009, 2011, 21605008, Coinvestigator, Molecular Chemical Strategy for Rare-Metal Materials Containing Platinum Which Contribute to Create Green Energy Systems, TANASE Tomoaki; NAKAJIMA Takayuki, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C), Nara Women's University, 4810000, 3700000, 1110000, Reactions of linear Pt and Pd clusters constrained by tri-and tetraphosphines with H^+and Lewis acidic Hg^<2+> were investigated, and copper-hydride clusters were synthesized as base metallic materials by using tetraphosphine ligands., url
  • Grant-in-Aid for Scientific Research (B), 2006, 2008, 18350030, Coinvestigator, Design of Multimetal Synergistic Systems with Linear Tetraphosphines and Their Use to Create Quantum Units, TANASE Tomoaki; NAKAJIMA Takayuki, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (B), Nara Women's University, 15990000, 14400000, 1590000, 直鎖状に供与原子が配列した四座ホスフィンを合成し、それらを用いて種々の低原子価金属種との反応により1~2 nm の大きさを持つ様々な形状の遷移金属クラスターの合成を行い、詳細な構造や物性を明らかにするとともに、多金属中心の協同効果に基づく現象の発現や量子ユニット創製のための端緒を得るべく基礎的研究を行った。特に、白金やパラジウムでは直鎖状クラスター(Pt_6, Pd_8)を、また、金、銀、銅の貨幣金属を用いた場合には環状クラスター(Au_6,Au_6Cu_2, Au_4Cu_4, Au_4Ag_2Cu_2)を構築することができ、分子レベルでの構造や物性を明らかにするとともに、これらを構造単位としたナノ構造構築を目指し研究を行った。, url
  • Grant-in-Aid for Young Scientists (B), 2006, 2007, 18750053, Principal investigator, 有機金属多核クラスターを基本骨格とする超分子化合物の合成研究, 中島 隆行, Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research Grant-in-Aid for Young Scientists (B), 3700000, 3700000, 遷移金属錯体は、新規触媒反応の開発といった利用に止まらず、近年金属の多様な配位能や結合様式を利用して、分子認識や光、磁気材料などの機能性材料としての応用が盛んに研究されてきている。 特に、超分子化学の分野では遷移金属錯体を利用し、遷移金属のd軌道の存在により生まれる四面体、平面正方形、八面体等といった幾何学的構造の多様性と、遷移金属と配位子との可逆的な相互作用を利用する事により通常の有機化学の手法を用いたのでは合成困難な多様な構造を有する化合物を一挙に構築している。金属錯体は酸化還元による金属イオンの酸化数の変化をともなう電子機能、d電子の不対スピンに起因する磁気特性、多様な電子遷移に基づく可視領域での色の変化などの特徴を有している事から遷移金属を基本骨格に有する超分子科学の研究は、非常に精力的に行われている。しかし、金属錯体を用いる超分子錯体の研究は、単核の金属錯体を用いたものばかりで、金属-金属結合を持つ有機金属多核クラスターを基本骨格に持つ超分子錯体の合成例は、ほとんど見られない。有機金属多核クラスターは、単核の錯体に見られない多電子移動、磁気的特性を有する事から新しい機能性を超分子化合物に付与する事が期待される。申請者は、上記の研究目的に基づきジエタノールアミン類を配位子とする多核金属クラスターの合成研究を行ってきた。今回、3-[benzyl (2-hydroxyethyl) amino]-1-propanol (LH_2)を配位子として用いることによりニッケル及びコバルトの4核錯体M_4L_2(OAc)_2(MeOH)_2が得られてくることを見出している。ここで,容易に交換可能なメタノール部位を他のアルコール系配位子に置換可能なことが分かった。 そこで,ジオールを用いることにより4核骨格を集積化した直鎖状クラスターが合成することを明らかにし,当初の目標として設定した多核クラスターを基本骨格に持つ超分子錯体の合成を達成することができた。
  • Apr. 2010, Mar. 2011, 金属多核錯体を基本骨格とするボトムアップ型ナノクラスターの創製, 公益財団法人 日立財団, 倉田奨励金
  • Jun. 2009, May 2010, 自己集積型超分子多核クラスターの合成研究-ボトムアップ型ナノクラスターの創製, 財団法人 徳山科学技術振興財団, 研究助成

Ⅲ.社会連携活動実績

1.公的団体の委員等(審議会、国家試験委員、他大学評価委員,科研費審査委員等)

  • Mar. 2019, Mar. 2021
  • Mar. 2009, Mar. 2011, Society


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