Synthesis and Reactions of Electron-deficient Metal Hydride

• Project/Area Number: 18350036
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Tokyo Institute of Technology (2008); Institute for Molecular Science (2006-2007)
• Principal Investigator: KAWAGUCHI Hiroyuki Tokyo Institute of Technology, 大学院・理工学研究科, 教授 (20262850)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥17,390,000 (Direct Cost: ¥14,600,000、Indirect Cost: ¥2,790,000); Fiscal Year 2008: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000); Fiscal Year 2007: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000); Fiscal Year 2006: ¥5,300,000 (Direct Cost: ¥5,300,000)
• Keywords: 高原子価錯体 / ヒドリド錯体 / アリールオキシド配位子 / 多座配位子 / ニオブ / タンタル / アリールオキシド錯体 / ニトリド錯体 / 金属間結合 / フェノキシド錯体 / ヒドリド配位子 / 2核錯体 / キレート錯体 / カルベン錯体

Research Abstract

3脚型補アリールオキシド配位子をもつニオブ錯体(Net_3H){[O_3]NbCl_3}を合成した。この錯体にKBHEt_3を反応させると2核ヒドリド錯体[K(dme)_2]_2{[O_3]_2Nb_2(μ-H)_4}が得られる。この錯体は窒素雰囲気下で、水素分子の発生を伴いながら、窒素分子のN≡N3重結合を切断し、ニトリド錯体[K(thf)_2]_2[{(O_3)Nb}_2(μ-N)_2]へと変化する。

Research Products

• [Journal Article] Reductive Coupling of Six Carbon Monoxides by a Ditantalum Hydride Complex (2009)
  • Author(s): T. Watanabe, Y. Ishida, T. Matsuo, H. Kawaguchi
  • Journal Title: J. Am. Chem. Soc. 131 Pages: 3474-3475
  • Peer Reviewed
• [Journal Article] Self-assembling construction of a novel nanoscale heptacobalt complex with an S-shaped folding (2008)
  • Author(s): M. Kondo, S. Sugahara, Y. Nakamura, M. Miyazawa, S. Yasue, K. Maeda, F. Uchida, G. Sakane, and H. Kawaguchi
  • Journal Title: Cryst. Eng. Commun 10 Pages: 1516-1519
  • Peer Reviewed
• [Journal Article] The Copper(II)Complex with Two Didentate Schiff Base Ligands The Unique Rearrangment That Proceeds under Alcohol Vapor in The Solid State to Construct Noninclusion Structure (2008)
  • Author(s): Y. Shibuya, K. Nabari, M. Kondo, S. Yasue, K. Maeda, F. Uchida, and H. Kawaguchi
  • Journal Title: Chem. Lett 37 Pages: 78-79
  • NAID: 10020148015
  • Peer Reviewed
• [Journal Article] The Copper(II) Complex with Two Didentate Schiff Base Ligands. The Unique Rearrangment That Proceeds under Alcohol Vapor in The Solid State to Construct Noninclusion Structure (2008)
  • Author(s): Y. Shibuya, K. Nabari, M. Kondo, S. Yasue, K. Maeda, F. Uchida, H. Kawaguchi
  • Journal Title: Chem. Lett. 37 Pages: 78-79
  • NAID: 10020148015
  • Peer Reviewed
• [Journal Article] Self-assembling Construction of a Novel Nanoscale Heptacobalt Complex with an S-shaped Folding (2008)
  • Author(s): M. Kondo, S. Sugahara, Y. Nakamura, M. Miyazawa, s. Yasue, K. Maeda, F. Uchida, G. Sakane
  • Journal Title: Cryst. Eng. Commun. 10 Pages: 1516-1519
  • Peer Reviewed
• [Journal Article] Dinitrogen Cleavage by a Diniobium Tetrahydride Complex : Formation of a Nitride and Its Conversion to Imide Species (2007)
  • Author(s): F. Akagi, T. Matsuo, and H.Kawaguchi
  • Journal Title: Angew. Chem., Int. Ed 46 Pages: 8778-8781
  • Peer Reviewed
• [Journal Article] Anisole-Diphenoxide Ligands and Their Zirconium Dichloride and Dialkyl Complexes (2007)
  • Author(s): T. Matsuo, H. Kawaguchi
  • Journal Title: Inorg. Chem 46 Pages: 8426-8434
  • Peer Reviewed
• [Journal Article] Biicosahedral Gold Clusters [Au_<25>(PPh_3)_<10>(SCnH_<2n+1>)_5Cl_2]^<2+>(n=2-18) : A Stepping Stone to Cluster-Assembled Materials (2007)
  • Author(s): Y. Shichibu, Y. Negishi, T. Watanabe, N. K. Chaki, H. Kawaguchi, T. Tsukuda
  • Journal Title: J. Phys. Chem 111 Pages: 7845-7847
  • Peer Reviewed
• [Journal Article] Synthesis, crystal structure and photoluminescence property of zinc(II), cadmium(II), and lead(II)complexes with bidentate ligand : 1-(1-imidazolyl)-4-(imidazol-1-ylmethyl)benz ene(IIMB) (2007)
  • Author(s): Q. Chu, L.-Y. Kong, T. Okamura, H. Kawaguchi, W.-L. Meng, W.-Y. Sun, and N. Ueyama, Z
  • Journal Title: Anorg. Allg. Chem 633 Pages: 326-331
  • Peer Reviewed
• [Journal Article] Unusual One-Dimensional Branched-Chain Structures Assembled by a Novel Imidazole-Containing Tripodal Ligand with Cadmium(II)Salts and Their Fluorescent Property (2007)
  • Author(s): L.-Y. Kong, X.-H. Lu, Y.-Q. Huang,H. Kawaguchi, Q. Chu, H.-F. Zhu, W.-Y. Sun
  • Journal Title: J. Solid State Chem 180 Pages: 331-338
  • Peer Reviewed
• [Journal Article] Synthesis and Crystal Structure of Mn(II)and Zn(II)Complexes with 1,3,5-Tris(carboxymethoxyl)benzene Ligand (2007)
  • Author(s): G. Wu, Y. Wang, X.-F. Wang, H. Kawaguchi, W.-Y. Sun,
  • Journal Title: J. Chem. Cryst 37 Pages: 199-205
  • Peer Reviewed
• [Journal Article] [MoFe_3S_4]^<3+> and [MoFe_3S_4]^<2+> Cubane Clusters Containing a Pentamethylcyclopentadienyl Molybdenum Moiety (2007)
  • Author(s): T. Komuro, H. Kawaguchi, J. Lang, T. Nagasawa and K. Tatsumi,
  • Journal Title: J. Orgnanomet. Chem 692 Pages: 1-9
  • Peer Reviewed
• [Journal Article] Synthesis and Structural Determination of New Multidimensional Coordination Polymers with 4,4'-Oxybis(benzoate) Building Ligands : Construction of Coordination Polymers with Heteroorganic Bridges (2007)
  • Author(s): M Kondo, Y. Irie, M. Miyazawa, H. Kawaguchi, S. Yasue, K. Maeda and F. Uchida
  • Journal Title: J. Orgnanomet. Chem 692 Pages: 136-141
  • Peer Reviewed
• [Journal Article] Zirconium Complexes of the Tridentate Bis(aryloxide)-N-Heterocyclic-Carbene Ligand : Chloride and Alkyl Functionalized Derivatives (2007)
  • Author(s): D. Zhang, H. Aihara, T Watanabe, T. Matsuo, and H. Kawaguchi,
  • Journal Title: J. Orgnanomet. Chem 692 Pages: 234-242
  • Peer Reviewed
• [Journal Article] Synthesis and Crystal Structure of Mn(II)and Zn(II)Complexes with 1,3,5-Tris(cazboxymethoxyl)benzene Ligand (2007)
  • Author(s): Wu, G.;Wang, Y.;Wang, X.-F.;Kawaguchi, H.;Sun
  • Journal Title: J.Chem.Cryst. 37 Pages: 199-205
  • Peer Reviewed
• [Journal Article] Anisole-Diphenoxide Ligands and Their Zirconium Dichloride and Dialkyl Complexes (2007)
  • Author(s): Matsuo, T.;Kawaguchi, H
  • Journal Title: Inorg.Chem. 46 Pages: 8426-8434
  • Peer Reviewed
• [Journal Article] Dinitrogen Cleavage by a Diniobium Tetrahydride Complex:Formation of a Nitride and Its Conversion to Imide Species (2007)
  • Author(s): Akagi, F.;Matsuo, T.;Kawaguchi, H
  • Journal Title: Angew.Chem., Int.Ed. 46 Pages: 8778-8781
  • Peer Reviewed
• [Journal Article] Mono{hydrotris(mercaptoimidazolyl)borato} Complexes of Manganese(II), Iron(II), Cobalt(II), and Nickel(II)Halides (2006)
  • Author(s): S. Senda, Y Ohki, T. Hirayama, D. Toda, J.-L. Chen, T. Matsumoto, H. Kawaguchi and K. Tatsumi
  • Journal Title: Inorg. Chem 45 Pages: 9914-9925
  • Peer Reviewed
• [Journal Article] Deprotonation Attempts on Imidazolium Salt Tethered by Substituted Phenol and Construction of Its Magnesium Complex by Transmetalation (2006)
  • Author(s): D. Zhang and H. Kawaguchi
  • Journal Title: Organometallics 25 Pages: 5506-5509
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure and Magnetic Property of a Two-dimensional Herringbone-like Network with Praseodymium(III)Nitrate and 1-Bromo-3,5-bis(imidazol-1-ylmethyl)benzene(bib) (2006)
  • Author(s): W.-L. Meng, Z.-H. Zhang, Y Lv, H. Kawaguchi and W.-Y. Sun
  • Journal Title: Appl. Organomet. Chem 20 Pages: 399-403
  • Peer Reviewed
• [Journal Article] Molecular Cage, One-dimensional Tube and Two-dimensional Polycatenane Obtained from Reactions of Flexible Tripodal ligand 1, 3, 5-Tris(imidazol-1-ylmethyl)-2, 4, 6-trimethylbenzene with Copper Salts (2006)
  • Author(s): W.-L. Meng, J. Fan, T.-a. Okamura, H. Kawaguchi, Y. Lv, W.-Y. Sun and N. Ueyama, Z
  • Journal Title: Anorg. Allg. Chem 632 Pages: 1890-1896
  • Peer Reviewed
• [Journal Article] Syntheses, Crystal Structures, and Magnetic Properties of Novel Copper(II)Complexes with the Flexible Bidentate Ligand 1-Bromo-3,5-bis(imidazol-1-ylmethyl)benzen (2006)
  • Author(s): W.-L. Meng, G.-X. Liu, T.-a. Okamura, H. Kawaguchi, Z.-H. Zhang, W.-Y. Sun and N. Ueyama
  • Journal Title: Cryst. Growth Des 6 Pages: 2092-2102
  • Peer Reviewed
• [Journal Article] From Carbon Dioxide to Methane : Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-Borane Complexes (2006)
  • Author(s): T. Matsuo, H. Kawaguchi
  • Journal Title: J. Am. Chem. Soc 128 Pages: 12362-12363
  • Peer Reviewed
• [Journal Article] A Tantalum(V)Carbene Complex : Formation of a Carbene-Bis(phenoxide)Ligand by Sequential Proton and Hydride Abstraction (2006)
  • Author(s): T. Watanabe, T. Matsuo and H. Kawaguchi
  • Journal Title: Inorg. Chem 45 Pages: 6580-6582
  • Peer Reviewed
• [Journal Article] A Tantalum(V) Carbene Complex : Formation of a Carbene-Bis(phenoxide) Ligand by Sequential Proton and Hydride Abstraction (2006)
  • Author(s): T.Watanabe, T.Matsuo, H.Kawaguchi
  • Journal Title: Inorg. Chem. 45 Pages: 17198-17199
• [Journal Article] From Carbon Dioxide to Methane : Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-_Borane Complexes (2006)
  • Author(s): T.Matsuo, H.Kawaguchi
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 12362-12363
• [Journal Article] Deprotonation Attempts on Imidazolium Salt Tethered by Substituted Phenol and Construction of Its Magnesium Complex by Transmetalation (2006)
  • Author(s): D.Zhang, H.Kawaguchi
  • Journal Title: Organometallics 25 Pages: 5506-5509
• [Journal Article] Mono{hydrotris(mercaptoimidazolyl)borato} Complexes of Manganese(II), Iron(II), Cobalt(II), and Nickel(II) Halides (2006)
  • Author(s): S.Senda, Y Ohki, T.Hirayama, D.Toda, J.-L.Chen, T.Matsumoto, H.Kawaguchi, K.Tatsumi
  • Journal Title: Inorg. Chem 45 Pages: 9914-9925
• [Journal Article] Zirconium Complexes of the Tridentate Bis(aryloxide)-N-Heterocyclic-Carbene Ligand : Chloride and Alkyl Functionalized Derivatives (2006)
  • Author(s): D.Zhang, H.Aihara, T Watanabe, T.Matsuo, H.Kawaguchi
  • Journal Title: J. Organomet. Chem. 692 Pages: 234-242
• [Presentation] フェノキシド多座配位子を用いた多核錯体反応場の構築と反応 (2008)
  • Author(s): 川口博之
  • Organizer: 第58回錯体化学討論会、シンポジウム「ヘテロ元素架橋多核サイトでの特異な反応性
  • Place of Presentation: 金沢
  • Year and Date: 2008-09-20
• [Presentation] フェノキシド多座配位子を用いた多核錯体反応場の構築と反応 (2008)
  • Author(s): 川口博之
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
  • Year and Date: 2008-09-20
• [Presentation] 遷移金属ヒドリド錯体による小分子活性化-配位子の効果- (2008)
  • Author(s): 川口博之
  • Organizer: 分子研研究会「配位子場制御に基づく機能性錯体の創成と応用-生体から触媒およびデバイスまで-
  • Place of Presentation: 岡崎
  • Year and Date: 2008-07-18
• [Presentation] Activation of Small Molecues by Niobium Complexes Having Triphenoxide Ligands (2007)
  • Author(s): H. Kawaguchi
  • Organizer: Workshop on Bioinorganic and Organometallic Perspectives in Activation of Small Molecules
  • Place of Presentation: 岡崎
  • Year and Date: 2007-11-18
• [Presentation] フェノキシドーチオフェノキシド混合型2座配位子を用いた4族遷移金属錯体の合成 (2007)
  • Author(s): 冨川 友秀・松尾 司・川口 博之
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋工業大学
  • Year and Date: 2007-09-25
• [Presentation] Benzylidene-bridged Diziroconium Complexes Supported by Anisole-diphenoxide Ligands (2007)
  • Author(s): H. Kawaguchi
  • Organizer: The First Asian Conference on Coordination Chemistry
  • Place of Presentation: 岡崎
  • Year and Date: 2007-07-30
• [Presentation] 還元系フェノキシド錯体による小分子活性化 (2007)
  • Author(s): 川口博之
  • Organizer: 分子研研究会「金属と分子集合-新領域創成をめざして-」
  • Place of Presentation: 岡崎
• [Presentation] Early Transition Metal Complexes Bearing Phenoxide Multidentate Ligands (2006)
  • Author(s): H. Kawaguchi
  • Organizer: 2006 Workshop on Organometallic Chemistry
  • Place of Presentation: 宇治
  • Year and Date: 2006-12-01
• [Presentation] Early Transition Metal Complexes Supported by Multidentate Phenoxide Ligands (2006)
  • Author(s): H. Kawaguchi
  • Organizer: The Sixth China-Japan Joint Symposium on Metal Cluster Compounds(CJSMCC-2006)
  • Place of Presentation: Huangshan(China)
  • Year and Date: 2006-10-23
• [Presentation] 多座フェノキシド配位子をもつ前周期遷移金属錯体の化学 : 合成と反応性 (2006)
  • Author(s): 川口博之
  • Organizer: 第39回有機金属若手の回夏の学校
  • Place of Presentation: 京都
  • Year and Date: 2006-07-12
• [Presentation] 4および5族遷移金属フェノキシド錯体による小分子活性化 (2006)
  • Author(s): 川口博之
  • Organizer: 第98回触媒討論会
  • Place of Presentation: 富山
  • Year and Date: 2006-06-29