1997 年度実績報告書

小分子の特異な活性化を目指した金属反応場の構築

研究課題

研究課題/領域番号	09102004
研究機関	東京大学
研究代表者	干鯛眞信東京大学, 大学院・工学系研究科, 教授 (60011011)
研究分担者	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) 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, 講師 (40193263) 溝部裕司東京大学, 生産技術研究所, 助教授 (40175609)
キーワード	窒素錯体 / ピロール / モリブデン / タングステン / アンモニア / カルコゲニドクラスター / 硫黄 / 多核錯体
研究概要	我々はこれまでの研究で、有機ホスフィンを補助配位子とするモリブデンおよびタングステンの窒素錯体について、その配位窒素分子をピロールおよびアミノピロールへと変換するとともに原料である窒素錯体を再生するサイクルを完成させている。今年度はこの反応を触媒的に進行させるための手段として、ヒドラジド錯体の生成やN-N,N-W(Mo)結合の開裂の際に必要な水素を、近傍の他の金属サイトで活性化された水素分子から供給できるような多核金属反応場を設計を行ってきた。実際、本研究においてカチオン性ルテニウム錯体[RuCl(dppp)_<>]^+を水素の活性化サイトとして用いることで、常圧水素下55℃という穏和な条件のもとでタングステン窒素錯体[W(N_2)_2(PMe_2Ph)_4]からアンモニア、アジンを合成できることが判明し、触媒的な窒素固定反応への展開の可能性を示すことができた。カルコゲニドクラスターの合成と反応性についても、[Cp^IrCl(μ-SH)_2IrCp^Cl]、[(Et_2NCS_2)Mo-S(μ-S)_2MoS(S_2CNEt_2)]のようなメタロリガンドをクラスター合成ユニットとして利用する合成法の開発により、各種の貴金属カルコゲニドクラスターの合理的合成を行うことができた。今後は貴金属の種類やクラスター構造を自在に制御しつつ、さらに多核の構造を有するクラスター合成まで展開するとともに、本研究で見出された新規クラスターの小分子に対する反応性、触媒活性の開拓を行っていく。

研究成果
(17件)

すべてその他

すべて文献書誌 (17件)

[文献書誌] H.Seino: "Synthesis and Structure Determination of Complexes Containing a Five-Membered Lactam Structures Based on Organohydradizo(2-)Ligands" Inorg.Chem.36. 162-171 (1997)
[文献書誌] Z.Tang: "The hydrosulfido-Bridges Diiridium and Dirhodium Complexes [Cp^*MCl(μ_2-SH)_2MCp^*Cl](M=Ir,Rh; Cp^*=η_5-C_5Me_5)as Versatile Precursors for Tri- and Tetranuclear Sulfido Clusters" Organometallics. 16. 151-154 (1997)
[文献書誌] Y.Nishibayashi: "Synthesis,Structures,and Reactivities of Rhodium and Ruthenium Complexes with a Novel Chiral Cyclopentadienyl-Ferrocenyldiphenylphosphine Bidentate Ligand" Organometallics. 16. 3091-3093 (1997)
[文献書誌] Y.Takagi: "Synthesis and Reactivities of cationic Diruthenium Complexes with Terminal Vinylidene Ligands. Hydration and Novel Cyclization of Acetylenes on the Diruthenium Center" Organometallics. 16. 4445-4452 (1997)
[文献書誌] S.Kuwata: "Structural Diversity of Tetranuclear Tungsten Sulfide Clusters : Syntheses and Crystal Structures of Cluster Containing Raft-Type W_4(μ_3-S)_2(μ-S)_4 and Tetrahedral W_4(μ-S)_6 Cores" J.Chem.Soc.,Dalton Trans.1753-1758 (1997)
[文献書誌] Y.Nishibayashi: "Allylation of Arenes Catalysed by Thiolate-Bridged Diruthenium Complexes" Chem.Commun.859-860 (1997)
[文献書誌] Y.Ishii: "Selective Hydroforylation of Internal Acetylenes by PdCl_2(PCy_3)_2 : Remarkable Synergistic Effect Cobalt" J.Am.Chem.Soc.119. 6448-6449 (1997)
[文献書誌] M.Nishio: "Preparation of a series of Dinuclear Ir(III)and Ir(II)Complexes Containing Bridging Thiolate Ligands" Inorg.Chim.Acta. 263. 119-123 (1997)
[文献書誌] M.Nishio: "Synthesis of Diiridium Complexes Containing Bridging Thiolate and Thioether Ligands[(η_5-C_5Me_5)Ir(-SR)(-MeSR)Ir(η_5-C_5Me_5)][OSO_2CF_3 and Their Reactivities Toward CO and H_2" Inorg.Chim.Acta. 265. 59-63 (1997)
[文献書誌] Y.Nishibayashi: "Rhodium(I)0,Iridium(I)-,and Ruthenium(II)-catalyzed Asymmetric Transfer Hydrogenation of Ketones using Diferrocenyl Dichalcogenides as CHiral Ligands" J.Organomet.Chem.531. 13-18 (1997)
[文献書誌] Y.Nishibayashi: "Synthesis and Structure of Novel Chiral Oxazolinylferrocenes and Oxazolinylferrocenylphosphines,and their Rhodium(I)-complexes" J.Organomet.Chem.545-546. 381-398 (1997)
[文献書誌] 桑田繁樹: "開かれる金属-硫黄クラスターの化学" 現代化学. 5. 32-37 (1997)
[文献書誌] Y.Nishibayashi: "Bimetallic System for Nitrogen Fixation : Ruthenium-Assisted Protonation of Coordinated N_2 on Tungsten with H_2" Science. 279. 540-542 (1998)
[文献書誌] Z.Tang: "Syntheses,Structures and Properties of Hydrosulfido-Bridged Diiridium and Dirhodium Complexes [Cp^*MCl(μ_2-SH)_2MCp^*Cl]and[Cp^*MCl(μ_2-SH)_3MCp^*Cl]^+(M=Ir,Rh;Cp^*=η_5-C_5Me_5)" Inorg.Chim.Acta. 267. 73-79 (1998)
[文献書誌] Y.Harada: "Reactivities of Molybdenum and Tungsten Diazoalkane-Isocyanide Complexes Derived from Dinitrogen Compleses" Bull.Chem.Soc.Jpn.71. 183-190 (1998)
[文献書誌] H.Seino: "Reactivities of the Coordinated Organonitriles in Molybdenum and Tungsten Phosphine Complexes : Protonation of the Nitrile Carbon and Cleavage of the CN Triple Bond" Inorg.Chim.Acta. (in press). (1998)
[文献書誌] G.Nakamura: "Unprecedented Conversion of Benzylideneanilines into Arylisocyanides Promoted by a Low-Valent Molybdenum Complexes. X-ray Structure of[Mo(CNPh)(N_2)(Ph_2PCH_2CH_2PPh_2)_2]" Organometallics. (in press). (1998)

1997 年度実績報告書

小分子の特異な活性化を目指した金属反応場の構築

研究代表者

干鯛眞信東京大学, 大学院・工学系研究科, 教授 (60011011)

研究成果

[文献書誌] H.Seino: "Synthesis and Structure Determination of Complexes Containing a Five-Membered Lactam Structures Based on Organohydradizo(2-)Ligands" Inorg.Chem.36. 162-171 (1997)

[文献書誌] Z.Tang: "The hydrosulfido-Bridges Diiridium and Dirhodium Complexes [Cp^MCl(μ_2-SH)_2MCp^Cl](M=Ir,Rh; Cp^*=η_5-C_5Me_5)as Versatile Precursors for Tri- and Tetranuclear Sulfido Clusters" Organometallics. 16. 151-154 (1997)

[文献書誌] Y.Nishibayashi: "Synthesis,Structures,and Reactivities of Rhodium and Ruthenium Complexes with a Novel Chiral Cyclopentadienyl-Ferrocenyldiphenylphosphine Bidentate Ligand" Organometallics. 16. 3091-3093 (1997)

[文献書誌] Y.Takagi: "Synthesis and Reactivities of cationic Diruthenium Complexes with Terminal Vinylidene Ligands. Hydration and Novel Cyclization of Acetylenes on the Diruthenium Center" Organometallics. 16. 4445-4452 (1997)

[文献書誌] S.Kuwata: "Structural Diversity of Tetranuclear Tungsten Sulfide Clusters : Syntheses and Crystal Structures of Cluster Containing Raft-Type W_4(μ_3-S)_2(μ-S)_4 and Tetrahedral W_4(μ-S)_6 Cores" J.Chem.Soc.,Dalton Trans.1753-1758 (1997)

[文献書誌] Y.Nishibayashi: "Allylation of Arenes Catalysed by Thiolate-Bridged Diruthenium Complexes" Chem.Commun.859-860 (1997)

[文献書誌] Y.Ishii: "Selective Hydroforylation of Internal Acetylenes by PdCl_2(PCy_3)_2 : Remarkable Synergistic Effect Cobalt" J.Am.Chem.Soc.119. 6448-6449 (1997)

[文献書誌] M.Nishio: "Preparation of a series of Dinuclear Ir(III)and Ir(II)Complexes Containing Bridging Thiolate Ligands" Inorg.Chim.Acta. 263. 119-123 (1997)

[文献書誌] M.Nishio: "Synthesis of Diiridium Complexes Containing Bridging Thiolate and Thioether Ligands[(η_5-C_5Me_5)Ir(-SR)(-MeSR)Ir(η_5-C_5Me_5)][OSO_2CF_3 and Their Reactivities Toward CO and H_2" Inorg.Chim.Acta. 265. 59-63 (1997)

[文献書誌] Y.Nishibayashi: "Rhodium(I)0,Iridium(I)-,and Ruthenium(II)-catalyzed Asymmetric Transfer Hydrogenation of Ketones using Diferrocenyl Dichalcogenides as CHiral Ligands" J.Organomet.Chem.531. 13-18 (1997)

[文献書誌] Y.Nishibayashi: "Synthesis and Structure of Novel Chiral Oxazolinylferrocenes and Oxazolinylferrocenylphosphines,and their Rhodium(I)-complexes" J.Organomet.Chem.545-546. 381-398 (1997)

[文献書誌] 桑田繁樹: "開かれる金属-硫黄クラスターの化学" 現代化学. 5. 32-37 (1997)

[文献書誌] Y.Nishibayashi: "Bimetallic System for Nitrogen Fixation : Ruthenium-Assisted Protonation of Coordinated N_2 on Tungsten with H_2" Science. 279. 540-542 (1998)

[文献書誌] Z.Tang: "Syntheses,Structures and Properties of Hydrosulfido-Bridged Diiridium and Dirhodium Complexes [Cp^MCl(μ_2-SH)_2MCp^Cl]and[Cp^MCl(μ_2-SH)_3MCp^Cl]^+(M=Ir,Rh;Cp^*=η_5-C_5Me_5)" Inorg.Chim.Acta. 267. 73-79 (1998)

[文献書誌] Y.Harada: "Reactivities of Molybdenum and Tungsten Diazoalkane-Isocyanide Complexes Derived from Dinitrogen Compleses" Bull.Chem.Soc.Jpn.71. 183-190 (1998)

[文献書誌] H.Seino: "Reactivities of the Coordinated Organonitriles in Molybdenum and Tungsten Phosphine Complexes : Protonation of the Nitrile Carbon and Cleavage of the CN Triple Bond" Inorg.Chim.Acta. (in press). (1998)

[文献書誌] G.Nakamura: "Unprecedented Conversion of Benzylideneanilines into Arylisocyanides Promoted by a Low-Valent Molybdenum Complexes. X-ray Structure of[Mo(CNPh)(N_2)(Ph_2PCH_2CH_2PPh_2)_2]" Organometallics. (in press). (1998)

1997 年度 実績報告書

小分子の特異な活性化を目指した金属反応場の構築

研究代表者

干鯛 眞信 東京大学, 大学院・工学系研究科, 教授 (60011011)

研究成果

[文献書誌] H.Seino: "Synthesis and Structure Determination of Complexes Containing a Five-Membered Lactam Structures Based on Organohydradizo(2-)Ligands" Inorg.Chem.36. 162-171 (1997)

[文献書誌] Z.Tang: "The hydrosulfido-Bridges Diiridium and Dirhodium Complexes [Cp^*MCl(μ_2-SH)_2MCp^*Cl](M=Ir,Rh; Cp^*=η_5-C_5Me_5)as Versatile Precursors for Tri- and Tetranuclear Sulfido Clusters" Organometallics. 16. 151-154 (1997)

[文献書誌] Y.Nishibayashi: "Synthesis,Structures,and Reactivities of Rhodium and Ruthenium Complexes with a Novel Chiral Cyclopentadienyl-Ferrocenyldiphenylphosphine Bidentate Ligand" Organometallics. 16. 3091-3093 (1997)

[文献書誌] Y.Takagi: "Synthesis and Reactivities of cationic Diruthenium Complexes with Terminal Vinylidene Ligands. Hydration and Novel Cyclization of Acetylenes on the Diruthenium Center" Organometallics. 16. 4445-4452 (1997)

[文献書誌] S.Kuwata: "Structural Diversity of Tetranuclear Tungsten Sulfide Clusters : Syntheses and Crystal Structures of Cluster Containing Raft-Type W_4(μ_3-S)_2(μ-S)_4 and Tetrahedral W_4(μ-S)_6 Cores" J.Chem.Soc.,Dalton Trans.1753-1758 (1997)

[文献書誌] Y.Nishibayashi: "Allylation of Arenes Catalysed by Thiolate-Bridged Diruthenium Complexes" Chem.Commun.859-860 (1997)

[文献書誌] Y.Ishii: "Selective Hydroforylation of Internal Acetylenes by PdCl_2(PCy_3)_2 : Remarkable Synergistic Effect Cobalt" J.Am.Chem.Soc.119. 6448-6449 (1997)

[文献書誌] M.Nishio: "Preparation of a series of Dinuclear Ir(III)and Ir(II)Complexes Containing Bridging Thiolate Ligands" Inorg.Chim.Acta. 263. 119-123 (1997)

[文献書誌] M.Nishio: "Synthesis of Diiridium Complexes Containing Bridging Thiolate and Thioether Ligands[(η_5-C_5Me_5)Ir(-SR)(-MeSR)Ir(η_5-C_5Me_5)][OSO_2CF_3 and Their Reactivities Toward CO and H_2" Inorg.Chim.Acta. 265. 59-63 (1997)

[文献書誌] Y.Nishibayashi: "Rhodium(I)0,Iridium(I)-,and Ruthenium(II)-catalyzed Asymmetric Transfer Hydrogenation of Ketones using Diferrocenyl Dichalcogenides as CHiral Ligands" J.Organomet.Chem.531. 13-18 (1997)

[文献書誌] Y.Nishibayashi: "Synthesis and Structure of Novel Chiral Oxazolinylferrocenes and Oxazolinylferrocenylphosphines,and their Rhodium(I)-complexes" J.Organomet.Chem.545-546. 381-398 (1997)

[文献書誌] 桑田繁樹: "開かれる金属-硫黄クラスターの化学" 現代化学. 5. 32-37 (1997)

[文献書誌] Y.Nishibayashi: "Bimetallic System for Nitrogen Fixation : Ruthenium-Assisted Protonation of Coordinated N_2 on Tungsten with H_2" Science. 279. 540-542 (1998)

[文献書誌] Z.Tang: "Syntheses,Structures and Properties of Hydrosulfido-Bridged Diiridium and Dirhodium Complexes [Cp^*MCl(μ_2-SH)_2MCp^*Cl]and[Cp^*MCl(μ_2-SH)_3MCp^*Cl]^+(M=Ir,Rh;Cp^*=η_5-C_5Me_5)" Inorg.Chim.Acta. 267. 73-79 (1998)

[文献書誌] Y.Harada: "Reactivities of Molybdenum and Tungsten Diazoalkane-Isocyanide Complexes Derived from Dinitrogen Compleses" Bull.Chem.Soc.Jpn.71. 183-190 (1998)

[文献書誌] H.Seino: "Reactivities of the Coordinated Organonitriles in Molybdenum and Tungsten Phosphine Complexes : Protonation of the Nitrile Carbon and Cleavage of the CN Triple Bond" Inorg.Chim.Acta. (in press). (1998)

[文献書誌] G.Nakamura: "Unprecedented Conversion of Benzylideneanilines into Arylisocyanides Promoted by a Low-Valent Molybdenum Complexes. X-ray Structure of[Mo(CNPh)(N_2)(Ph_2PCH_2CH_2PPh_2)_2]" Organometallics. (in press). (1998)

1997 年度実績報告書

干鯛眞信東京大学, 大学院・工学系研究科, 教授 (60011011)

[文献書誌] Z.Tang: "The hydrosulfido-Bridges Diiridium and Dirhodium Complexes [Cp^MCl(μ_2-SH)_2MCp^Cl](M=Ir,Rh; Cp^*=η_5-C_5Me_5)as Versatile Precursors for Tri- and Tetranuclear Sulfido Clusters" Organometallics. 16. 151-154 (1997)

[文献書誌] Z.Tang: "Syntheses,Structures and Properties of Hydrosulfido-Bridged Diiridium and Dirhodium Complexes [Cp^MCl(μ_2-SH)_2MCp^Cl]and[Cp^MCl(μ_2-SH)_3MCp^Cl]^+(M=Ir,Rh;Cp^*=η_5-C_5Me_5)" Inorg.Chim.Acta. 267. 73-79 (1998)