1999 Fiscal Year Annual Research Report

小分子の特異な活性化を目指した金属反応場の構築

Research Project

Project/Area Number	09102004
Research Institution	The University of Tokyo
Principal Investigator	干鯛眞信東京大学, 大学院・工学系研究科, 教授 (60011011)
Co-Investigator(Kenkyū-buntansha)	西林仁昭東京大学, 大学院・工学系研究科, 助手 (40282579) 石井洋一東京大学, 大学院・工学系研究科, 助教授 (40193263) 溝部裕司東京大学, 生産技術研究所, 助教授 (40175609) 清野秀岳東京大学, 生産技術研究所, 助手 (50292751) 桑田繁樹東京大学, 大学院・工学系研究科, 助手 (10292781)
Keywords	窒素錯体 / アンモニア / モリブデン / タングステン / 硫黄 / 多核錯体 / カルコゲニドクラスター / 触媒反応
Research Abstract	我々は平成10年度までの研究において既に、55℃24時間という非常に温和な条件下でルテニウムカチオン性水素錯体とタングステン窒素錯体とを反応させることで配位窒素分子をアンモニアに変換できることを明らかにしている。今年度はルテニウム水素錯体の代りに、硫黄架橋二核モリブデン錯体を用いて水素を活性化させ、室温でも配位窒素からアンモニアが生成することを明らかにした。上記の反応では活性化された水素分子の一つの水素原子のみが反応に利用されているが、本年度の研究により二つの水素原子が反応に関与する触媒反応が開発された。すなわち、触媒量のルテニウムカチオン性水素錯体存在下、シリルエノールエーテルを常圧の水素雰囲気下で反応させることにより対応するケトンとシランとが生成することを明らかにした。窒素固定酵素の活性部位の構造に関連した金属クラスターの合成に関しては、Ir2Mo2S2キュバン型クラスター骨格と有機ヒドラジンの反応によりヒドラジド配位子を有する遷移金属-硫黄クラスターを合成することに成功した。また、平成10年度までの研究で開発してきたヒドロスルフィドあるいはスルフィド架橋二核錯体をビルディングブロックとする混合金属錯体の合成法を、4族、7族及び10族遷移金属を含む混合金属クラスター合成にも拡大適用することができた。このコンセプトは三種混合金属多核錯体の合成にも応用可能である。さらに、架橋配位子として硫黄の代りにセレンをもつ種々の硫黄類似クラスターを合成することにも成功した。硫黄架橋多核錯体上での触媒反応についても、新たにチオラート架橋二核ルテニウム錯体上でのプロパルギルアルコール類の位置選択的な求核置換反応を見出した。この反応は、この二核錯体上でのみ特異的に進行する新規な触媒反応である。

Research Products
(20 results)

All Other

All Publications (20 results)

[Publications] T. Amemiya: "Syntheses of Mixed-metal M_2Ti_2S_4 Cubane-type Sulfido Clusters (M=Ru, Rh, Ir, Cu) from a Dinuclear Organometallic Thiotitanate Anion"Chem. Commun.. 711-712 (1999)
[Publications] H. Ishino: "Synthesis and Structures of Tungsten (1-Pyridinio)imido Complexes and Their Facile N-N Bond Cleavage"Inorg. Chem.. 38. 2489-2496 (1999)
[Publications] I. Takei: "Iridium-Catalyzed Asymmetric Hydrosilylation of Imines Using Chiral Oxazolinyl-Phosphine Ligands"Organometallics. 18. 2271-2274 (1999)
[Publications] Y. Nishibayashi: "Extremely High Enantioselective Redox Reaction of Ketones and Alcohols Catalyzed by RuCl_2(PPh_3)(oxazolinylferrocenylphosphine)"Organometallics. 18. 2291-2293 (1999)
[Publications] T. Iwasa: "Preparation of Cationic Dinuclear Hydrido Complexes of Ruthenium, Rhodium, and Iridium with Bridging Thiolato Ligands and Their Reactions with Nitrosobenzene"Inorg. Chem.. 38. 2851-2859 (1999)
[Publications] S. Kabashima: "Electron-Deficient Early-Late Heterobimetallic Sulfido Clusters. Unusual Reactivities of Ti_2Ru_2S_4 Cubane-type Clusters with Four Cyclopentadienyl Colignds"J. Am. Chem. Soc.. 121. 7837-7845 (1999)
[Publications] C. Arita: "Formation of Novel Tetradentate Phosphine Ligand o-C_6H_4(PPhCH_2CH_2PPh_2)_2 by Coupling of Two Diphosphine Ligands Bound to Low-Valent Mo or W Center"Chem. Lett.. 611-612 (1999)
[Publications] T. Kochi: "Synthesis and Reactivities of Ir_2Ru Heterobimetallic Sulfido Clusters Derived from a Hydrogensulfio-bridged Diiridium Complex"J. Chem. Soc., Dalton Trans.. 2575-2582 (1999)
[Publications] T. Kochi: "Rh_4S_7 and Ir_3CuS_6 Clusters with Di- and Trisulfido Ligands Derived from Dinuclear Hydrogensulfido Complexes"Chem. Lett.. 1279-1280 (1999)
[Publications] H. Seino: "Conversion of Benzaldehyde Imines into Isocyanides at a Low-Valent Molybdenum Center Preparation and Reactivities of Isocyanide-Dinitrogen Complexes"Organometallics. 18. 4165-4173 (1999)
[Publications] Y. Nishibayashi: "Novel Catalytic Hydrogenolysis of Trimethylsilyl Enol Ethers by the Use of an Acidic Ruthenium Dihydrogen Complex"Angew. Chem. Int. Ed. Engl.. 3047-3050 (1999)
[Publications] M. Taniguchi: "Hydrosulfurization of Benzothiophene over Zeolite-Supported Catalysts Prepared from Mo and Mo-Ni Sulfide Clusters"J. Catal.. 187. 139-150 (1999)
[Publications] S. Kabashima: "Crossed Condensation of Two Different Hydrosulfido-Bridged Dinuclear Complexes : Structures and Reactivities of TiRu_3S_4 Cubane-Type Sulfido Clusters"Angew. Chem. Int. Ed. Engl.. (印刷中).
[Publications] Y. Ishii: "Reactions of Cationic Dirhodium and Diiridium Complexes [Cp*M(μ-Cl)(μ-SPr)_2MCp*][Otf](M=Rh, Ir) with Terminal Alkynes"J. Oragnomet. Chem.. (印刷中).
[Publications] S. Matsukawa: "Syntheses, Structures, and Reactivities of Mono- and Dinuclear Iridium Thiolato Complexes Containing Nitrosyl Ligands"Inorg. Chem.. 39. 791-798 (2000)
[Publications] M. Hidai: "Synthesis and Reactivities of Cubane-Type Sulfido Clusters Containing Noble Metals"Acc. Chem. Res.. 33. 46-52 (2000)
[Publications] Y. Tanabe: "Reaction Mechanism of the C≡N Triple Bond Cleavage of β-Ketonitrile on a Molybdenum(0) Center"J. Am. Chem. Soc.. (印刷中).
[Publications] H. Seino: "Preparation of Sulfide-Bridged Di- or Trinuclear Pyrrolylimido and Diazoalkane Complexes Derived from a Tungsten Dinitrogen Complex"Bull. Chem. Soc. Jpn. (印刷中).
[Publications] S. Nagano: "Syntheses of Dinuclear Ir Complex Containing Bridging Tetraselenide Ligands [(C_5Me_5)Ir(μ-Se_4)_2Ir(C_5Me_5)]and its Conversion into Ir_2Pd_2Se_3 and Ir_2Pd_3Se_5"Chem. Commun. (印刷中).
[Publications] D. Masui: "Synthesis and Characterization of Mixed-Metal Sulfido Clusters with the Cubane-Type PtMo3S4 Core"Bull. Chem. Soc. Jpn. (印刷中).

1999 Fiscal Year Annual Research Report

小分子の特異な活性化を目指した金属反応場の構築

Principal Investigator

干鯛 眞信 東京大学, 大学院・工学系研究科, 教授 (60011011)

Research Products

[Publications] T. Amemiya: "Syntheses of Mixed-metal M_2Ti_2S_4 Cubane-type Sulfido Clusters (M=Ru, Rh, Ir, Cu) from a Dinuclear Organometallic Thiotitanate Anion"Chem. Commun.. 711-712 (1999)

[Publications] H. Ishino: "Synthesis and Structures of Tungsten (1-Pyridinio)imido Complexes and Their Facile N-N Bond Cleavage"Inorg. Chem.. 38. 2489-2496 (1999)

[Publications] I. Takei: "Iridium-Catalyzed Asymmetric Hydrosilylation of Imines Using Chiral Oxazolinyl-Phosphine Ligands"Organometallics. 18. 2271-2274 (1999)

[Publications] Y. Nishibayashi: "Extremely High Enantioselective Redox Reaction of Ketones and Alcohols Catalyzed by RuCl_2(PPh_3)(oxazolinylferrocenylphosphine)"Organometallics. 18. 2291-2293 (1999)

[Publications] T. Iwasa: "Preparation of Cationic Dinuclear Hydrido Complexes of Ruthenium, Rhodium, and Iridium with Bridging Thiolato Ligands and Their Reactions with Nitrosobenzene"Inorg. Chem.. 38. 2851-2859 (1999)

[Publications] S. Kabashima: "Electron-Deficient Early-Late Heterobimetallic Sulfido Clusters. Unusual Reactivities of Ti_2Ru_2S_4 Cubane-type Clusters with Four Cyclopentadienyl Colignds"J. Am. Chem. Soc.. 121. 7837-7845 (1999)

[Publications] C. Arita: "Formation of Novel Tetradentate Phosphine Ligand o-C_6H_4(PPhCH_2CH_2PPh_2)_2 by Coupling of Two Diphosphine Ligands Bound to Low-Valent Mo or W Center"Chem. Lett.. 611-612 (1999)

[Publications] T. Kochi: "Synthesis and Reactivities of Ir_2Ru Heterobimetallic Sulfido Clusters Derived from a Hydrogensulfio-bridged Diiridium Complex"J. Chem. Soc., Dalton Trans.. 2575-2582 (1999)

[Publications] T. Kochi: "Rh_4S_7 and Ir_3CuS_6 Clusters with Di- and Trisulfido Ligands Derived from Dinuclear Hydrogensulfido Complexes"Chem. Lett.. 1279-1280 (1999)

[Publications] H. Seino: "Conversion of Benzaldehyde Imines into Isocyanides at a Low-Valent Molybdenum Center Preparation and Reactivities of Isocyanide-Dinitrogen Complexes"Organometallics. 18. 4165-4173 (1999)

[Publications] Y. Nishibayashi: "Novel Catalytic Hydrogenolysis of Trimethylsilyl Enol Ethers by the Use of an Acidic Ruthenium Dihydrogen Complex"Angew. Chem. Int. Ed. Engl.. 3047-3050 (1999)

[Publications] M. Taniguchi: "Hydrosulfurization of Benzothiophene over Zeolite-Supported Catalysts Prepared from Mo and Mo-Ni Sulfide Clusters"J. Catal.. 187. 139-150 (1999)

[Publications] S. Kabashima: "Crossed Condensation of Two Different Hydrosulfido-Bridged Dinuclear Complexes : Structures and Reactivities of TiRu_3S_4 Cubane-Type Sulfido Clusters"Angew. Chem. Int. Ed. Engl.. (印刷中).

[Publications] Y. Ishii: "Reactions of Cationic Dirhodium and Diiridium Complexes [Cp*M(μ-Cl)(μ-SPr)_2MCp*][Otf](M=Rh, Ir) with Terminal Alkynes"J. Oragnomet. Chem.. (印刷中).

[Publications] S. Matsukawa: "Syntheses, Structures, and Reactivities of Mono- and Dinuclear Iridium Thiolato Complexes Containing Nitrosyl Ligands"Inorg. Chem.. 39. 791-798 (2000)

[Publications] M. Hidai: "Synthesis and Reactivities of Cubane-Type Sulfido Clusters Containing Noble Metals"Acc. Chem. Res.. 33. 46-52 (2000)

[Publications] Y. Tanabe: "Reaction Mechanism of the C≡N Triple Bond Cleavage of β-Ketonitrile on a Molybdenum(0) Center"J. Am. Chem. Soc.. (印刷中).

[Publications] H. Seino: "Preparation of Sulfide-Bridged Di- or Trinuclear Pyrrolylimido and Diazoalkane Complexes Derived from a Tungsten Dinitrogen Complex"Bull. Chem. Soc. Jpn. (印刷中).

[Publications] S. Nagano: "Syntheses of Dinuclear Ir Complex Containing Bridging Tetraselenide Ligands [(C_5Me_5)Ir(μ-Se_4)_2Ir(C_5Me_5)]and its Conversion into Ir_2Pd_2Se_3 and Ir_2Pd_3Se_5"Chem. Commun. (印刷中).

[Publications] D. Masui: "Synthesis and Characterization of Mixed-Metal Sulfido Clusters with the Cubane-Type PtMo3S4 Core"Bull. Chem. Soc. Jpn. (印刷中).

干鯛眞信東京大学, 大学院・工学系研究科, 教授 (60011011)

[Publications] Y. Ishii: "Reactions of Cationic Dirhodium and Diiridium Complexes [CpM(μ-Cl)(μ-SPr)_2MCp][Otf](M=Rh, Ir) with Terminal Alkynes"J. Oragnomet. Chem.. (印刷中).