1998 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, 助教授 (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	我々は平成9年度までの研究において既に,ルテニウムのカチオン性配位不飽和錯体[RuCl(diphosphine)_2]^+の存在下,常圧の水素分子によってタングステン窒素錯体cis-[W(N_2)_2(PMe_2Ph)_4]の配位窒素分子がアンモニアあるいはアジンに変換できることを明らかにしている.今年度は本反応系のルテニウム錯体上のホスフィン配位子などの効果について詳細に検討して反応系の最適化を試みた結果,l,2-ビス(ジフェニルホスフィノ)エタンを補助配位子に用いることで,窒素錯体あたり144%のアンモニア収率を達成した.一方,窒素固定酵素の作用機構モデルとなる反応として,タングステン窒素錯体と架橋ヒドロスルフィド錯体からのアンモニア生成反応を見出した. 新規反応場としての金属-硫黄多核錯体の合成においても,窒素固定酵素に関連する金属-硫黄錯体として,分子状窒素に直接由来する含窒素配位子であるジアゾアルカンおよび1-ピロリルイミド配位子をもつ多核タングステン硫黄錯体の合成に成功した.ま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族遷移金属を含む混合金属クラスターの合成にも適用することができた. さらに硫黄架橋多核錯体上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アルキン類のhead-to-head,cis選択的な二量化,あるいはパラジウム-ルテニウム混合金属三核硫黄クラスター上での内部フェニルアセチレン類へのアルコールの位置選択的な付加反応など,これらの多核錯体に特徴的な反応性を見出した.

研究成果

(24件)

すべてその他

すべて文献書誌 (24件)

[文献書誌] Y.Mizobe: "Syntheses of Ruthenium Hydridotris(1-pyrazoryl)borato Complexes Having Sulfur-Donor Coligands" Inorg.Chim.Acta. 273. 238-243 (1998)
[文献書誌] H.Ishino: "Synthesis of Boryldiazenido Complexes from Tungsten Dinitrogen Complexes" Chem.Lett.677-678 (1998)
[文献書誌] Y.Nishibayashi: "Ruthenium-Catalyzed Asymmetric Hydrosilylation of Ketones and Imine" Organometallics. 17. 3420-3422 (1998)
[文献書誌] S.Kuwata: "Structures and Reactivities of Diruthenium Dithiolene Complexes and Triruthenium Sulfido Clusters Derived from a Hydrosulfido-Bridged Diruthenium Complex" Organometallics. 17. 3429-3436 (1998)
[文献書誌] D.Masui: "Regioselective Addition of Alcohols to Internal 1-Aryl-1-alkynes Catalyzed by a Triangular Heterobimetallic Ir_2Pd Sulfido Cluster" Chem.Lett.717-718 (1998)
[文献書誌] S.Kuwata: "Hydrosulfido-Bridged Titanium-Ruthenium Heterobimetallic Complex : Stepwise Construction of Ti_2Ru_2S_4 Cubane-Type Sulfido Cluster" Chem.Lett.885-886 (1998)
[文献書誌] K.Takagahara: "Synthesis and Molecular Structure of Tetranuclear Tungusten-Gallium Complexes with Bridging Dinitrogen Ligands" Chem.Lett.897-898 (1998)
[文献書誌] Z.Tang: "Metal-Metal Bonding in Pentanuclear Bow-Tie Metal Sulfido Clusters. Synthetic and Structural Studies on the Cationic Pentanuclear Clusters[(Cp^*Ir)_2(μ_3-S)_2M(μ_3-S)_2(IrCp^*)_2]^<n+>(M=Fe,Co,Ni;n=1,2)" Inorg.Chem.37. 4909-4920 (1998)
[文献書誌] J.-P.Qu: "Head-to-head Z Dimerization of Terminal Alkynes Catalyzed by Thiolato-Bridged Diruthenium Complexes" Chem.Lett.1003-1004 (1998)
[文献書誌] Y.Nishibayashi: "A Model for Protonation of Dinitrogen by Nitrogenase : Protonation of Coordinated Dinitrogen on Tungsten with Hydrosulfido-Bridged Diruthenium Complexes" J.Am.Chem.Soc.120. 10559-10560 (1998)
[文献書誌] T.Sato: "Synthesis and Reactivities of the Indenyl-Ruthenium Cluster [(η^5-C_9H_7)Ru(μ-SEt)]_3 : Indenyl Effect in the Trinuclear Ruthenium Cluster" J.Organomet.Chem.569. 99-108 (1998)
[文献書誌] Y.Harada: "Syntheses of Tungsten Diazoalkane Complexes from a Dinitrogen Complex and Diketones. Conversion of Molecular Nitrogen into Pyrazoles via the Diazoalkane Complexes as Intermediates" Bull.Chem.Soc.Jpn.71. 2701-2708 (1998)
[文献書誌] T.Ikada: "Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M_2M′S_4(M=Mo,W;M′=Pd,Pt) and Tetrametallic Cubane-Type Mo_2Pd_2S_4 Cores" Inorg.Chem.37. 5793-5797 (1998)
[文献書誌] M.Retbφll: "Dinuclear Pyridine-1-Imine-Bridged Rhodium(III) Complexes. Intramolecular Carbon-Hydrogen Bond Activation" Chem.Lett.1217-1218 (1998)
[文献書誌] S.Matsukawa: "Reactions of Iridium and Ruthenium Arenethiolato Complexes with Propylene Sulfide. X-ray Structures of 1-Arylthio-2-Propanethiolato-S,S′ Iridium and Ruthenium Complexes" Inorg.Chem.Commun.1. 368-371 (1998)
[文献書誌] S.Takemoto: "Synthesis of Heterobimetallic Fe-M(M=Ni,Pd,Pt) Complexes Containing the 1,1′-Ferrocenedithiolato Ligand and Their Conversion to Trinuclear Complexes" Inorg.Chem.37. 6428-6434 (1998)
[文献書誌] T.Ikada: "Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Incomplete Cubane-Type M_2M′S_4 and Cubane-Type M_2M′_2S_4 Cores(M=Mo,W;M′=Rh,Ir)" Inorg.Chem.38. 64-69 (1999)
[文献書誌] M.Retbφll: "Synthesis and Reductive N-N Bond Cleavage of Neutral and Cationic Titanium(1-Pyridinio)imido Complexes" Organometallics. 18. 150-155 (1999)
[文献書誌] Y.Arikawa: "Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using Chiral Oxazolinylferrocenylphosphines and One of Their Ru(II) Complex" J.Organomet.Chem.572. 163-168 (1999)
[文献書誌] M.Hidai: "Chemical Nitrogen Fixation by Molybdenum and Tungsten Complexes" Coord.Chem.Rev.(in press). (1998)
[文献書誌] H.Ishino: "Synthesis and Structures of Tungsten(1-Pyridinio)imido Complexes and Their Facile N-N Bond Cleavage" Inorg.Chem.38(in press). (1999)
[文献書誌] Y.Harada: "Condensation of Triketones with Tungsten Hydrazido(2-) Complexes Derived from a Dinitrogen Complex : Formation of Mononuclear or Dinuclear Diazoalkane Complexes" J.Organomet.Chem.(in press). (1999)
[文献書誌] Y.Harada: "Syntheses and Structures of Tungsten Ferrocenyldiazoalkane Complexes Derived from a Dinitrogen Complex" Inorg.Chim.Acta. (in press). (1999)
[文献書誌] T.Sasagawa: "Selective N-N and W-N Bond Cleavage of Tungsten Pyrrolylimido Complexes Derived from Tungsten Dinitrogen Complex" Bull.Chem.Soc.Jpn.72(in press). (1999)

1998 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] Y.Mizobe: "Syntheses of Ruthenium Hydridotris(1-pyrazoryl)borato Complexes Having Sulfur-Donor Coligands" Inorg.Chim.Acta. 273. 238-243 (1998)

[文献書誌] H.Ishino: "Synthesis of Boryldiazenido Complexes from Tungsten Dinitrogen Complexes" Chem.Lett.677-678 (1998)

[文献書誌] Y.Nishibayashi: "Ruthenium-Catalyzed Asymmetric Hydrosilylation of Ketones and Imine" Organometallics. 17. 3420-3422 (1998)

[文献書誌] S.Kuwata: "Structures and Reactivities of Diruthenium Dithiolene Complexes and Triruthenium Sulfido Clusters Derived from a Hydrosulfido-Bridged Diruthenium Complex" Organometallics. 17. 3429-3436 (1998)

[文献書誌] D.Masui: "Regioselective Addition of Alcohols to Internal 1-Aryl-1-alkynes Catalyzed by a Triangular Heterobimetallic Ir_2Pd Sulfido Cluster" Chem.Lett.717-718 (1998)

[文献書誌] S.Kuwata: "Hydrosulfido-Bridged Titanium-Ruthenium Heterobimetallic Complex : Stepwise Construction of Ti_2Ru_2S_4 Cubane-Type Sulfido Cluster" Chem.Lett.885-886 (1998)

[文献書誌] K.Takagahara: "Synthesis and Molecular Structure of Tetranuclear Tungusten-Gallium Complexes with Bridging Dinitrogen Ligands" Chem.Lett.897-898 (1998)

[文献書誌] Z.Tang: "Metal-Metal Bonding in Pentanuclear Bow-Tie Metal Sulfido Clusters. Synthetic and Structural Studies on the Cationic Pentanuclear Clusters[(Cp^*Ir)_2(μ_3-S)_2M(μ_3-S)_2(IrCp^*)_2]^<n+>(M=Fe,Co,Ni;n=1,2)" Inorg.Chem.37. 4909-4920 (1998)

[文献書誌] J.-P.Qu: "Head-to-head Z Dimerization of Terminal Alkynes Catalyzed by Thiolato-Bridged Diruthenium Complexes" Chem.Lett.1003-1004 (1998)

[文献書誌] Y.Nishibayashi: "A Model for Protonation of Dinitrogen by Nitrogenase : Protonation of Coordinated Dinitrogen on Tungsten with Hydrosulfido-Bridged Diruthenium Complexes" J.Am.Chem.Soc.120. 10559-10560 (1998)

[文献書誌] T.Sato: "Synthesis and Reactivities of the Indenyl-Ruthenium Cluster [(η^5-C_9H_7)Ru(μ-SEt)]_3 : Indenyl Effect in the Trinuclear Ruthenium Cluster" J.Organomet.Chem.569. 99-108 (1998)

[文献書誌] Y.Harada: "Syntheses of Tungsten Diazoalkane Complexes from a Dinitrogen Complex and Diketones. Conversion of Molecular Nitrogen into Pyrazoles via the Diazoalkane Complexes as Intermediates" Bull.Chem.Soc.Jpn.71. 2701-2708 (1998)

[文献書誌] T.Ikada: "Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Trimetallic M_2M′S_4(M=Mo,W;M′=Pd,Pt) and Tetrametallic Cubane-Type Mo_2Pd_2S_4 Cores" Inorg.Chem.37. 5793-5797 (1998)

[文献書誌] M.Retbφll: "Dinuclear Pyridine-1-Imine-Bridged Rhodium(III) Complexes. Intramolecular Carbon-Hydrogen Bond Activation" Chem.Lett.1217-1218 (1998)

[文献書誌] S.Matsukawa: "Reactions of Iridium and Ruthenium Arenethiolato Complexes with Propylene Sulfide. X-ray Structures of 1-Arylthio-2-Propanethiolato-S,S′ Iridium and Ruthenium Complexes" Inorg.Chem.Commun.1. 368-371 (1998)

[文献書誌] S.Takemoto: "Synthesis of Heterobimetallic Fe-M(M=Ni,Pd,Pt) Complexes Containing the 1,1′-Ferrocenedithiolato Ligand and Their Conversion to Trinuclear Complexes" Inorg.Chem.37. 6428-6434 (1998)

[文献書誌] T.Ikada: "Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Incomplete Cubane-Type M_2M′S_4 and Cubane-Type M_2M′_2S_4 Cores(M=Mo,W;M′=Rh,Ir)" Inorg.Chem.38. 64-69 (1999)

[文献書誌] M.Retbφll: "Synthesis and Reductive N-N Bond Cleavage of Neutral and Cationic Titanium(1-Pyridinio)imido Complexes" Organometallics. 18. 150-155 (1999)

[文献書誌] Y.Arikawa: "Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using Chiral Oxazolinylferrocenylphosphines and One of Their Ru(II) Complex" J.Organomet.Chem.572. 163-168 (1999)

[文献書誌] M.Hidai: "Chemical Nitrogen Fixation by Molybdenum and Tungsten Complexes" Coord.Chem.Rev.(in press). (1998)

[文献書誌] H.Ishino: "Synthesis and Structures of Tungsten(1-Pyridinio)imido Complexes and Their Facile N-N Bond Cleavage" Inorg.Chem.38(in press). (1999)

[文献書誌] Y.Harada: "Condensation of Triketones with Tungsten Hydrazido(2-) Complexes Derived from a Dinitrogen Complex : Formation of Mononuclear or Dinuclear Diazoalkane Complexes" J.Organomet.Chem.(in press). (1999)

[文献書誌] Y.Harada: "Syntheses and Structures of Tungsten Ferrocenyldiazoalkane Complexes Derived from a Dinitrogen Complex" Inorg.Chim.Acta. (in press). (1999)

[文献書誌] T.Sasagawa: "Selective N-N and W-N Bond Cleavage of Tungsten Pyrrolylimido Complexes Derived from Tungsten Dinitrogen Complex" Bull.Chem.Soc.Jpn.72(in press). (1999)

1998 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: "Metal-Metal Bonding in Pentanuclear Bow-Tie Metal Sulfido Clusters. Synthetic and Structural Studies on the Cationic Pentanuclear Clusters[(Cp^Ir)_2(μ_3-S)_2M(μ_3-S)_2(IrCp^)_2]^<n+>(M=Fe,Co,Ni;n=1,2)" Inorg.Chem.37. 4909-4920 (1998)