1999 Fiscal Year Annual Research Report

有機遷移金属錯体の特性に根ざした選択的新反応・新触媒反応の開発

Research Project

Project/Area Number	09309006
Research Institution	Osaka University
Principal Investigator	谷一英大阪大学, 大学院・基礎工学研究科, 教授 (60029444)
Co-Investigator(Kenkyū-buntansha)	山縣恒明大阪大学, 大学院・基礎工学研究科, 助手 (70166594) 片岡靖隆大阪大学, 大学院・基礎工学研究科, 助手 (90221879) 真島和志大阪大学, 大学院・基礎工学研究科, 助教授 (70159143)
Keywords	パーアリールホスフィン / イリジウム / 水素移動型 / Cp'-P配位子 / ロジウム / 立体特異的 / タンタル / モノアザジエン
Research Abstract	パーアリールジホスフィン配位子であるBINAP[2,2'-bis(diphenylphosphino)1.1'-binaphtyl]を有するイリジウム二核錯体(昨年度本研究により合成方法を確立した)を用いるアセチレン誘導体などの不飽和化合物の触媒的水素移動型還元反応の開発に成功した。メタノール中、トランに2mol%の二核錯体を加え80℃に加熱し18時間反応させると、トランススチルベンが90%の収率で得られた。この時、10%のアルカンも得られた。本反応は水素源として、一般に水素移動型の反応で用いられているイソプロピルアルコールよりも安価なメタノールの方が有効であった。また、重水素実験よりメタノールの水酸基のプロトンだけでなくメチル基のプロトンも水素源となっていることがわかった。シクロペンタジエニル誘導体とホスフィノ基がキレートした配位子(Cp'-P配位子)が、金属周りの立体化学の制御に有効であることを明らかにした。光学活性Cp'-P配位子を有するロジウムカルボニル錯体(昨年度本研究により合成方法を確立した)に銀塩およびアセチレン化合物を反応させると、立体特異的かつ位置選択的にカチオン性アルケニルロジウム錯体が得られた。本反応では、4種類の異性体の生成が可能であるが、1種類の異性体のみが選択的に生成した。反応系中でロジウム周りの不斉点が全くラセミ化しておらず、Cp'-P配位子を有するロジウム錯体が不斉反応の触媒として利用できることがわかった。ブタジエンの1-位が1つの窒素原子で置換されたモノアザジエン配位子をもつCp^*Ta(monoazadiene)R_2型のタンタル錯体も合成し、その構造解析、反応性の検討を行った。

Research Products

(11 results)

All Other

All Publications (11 results)

[Publications] 中山祐正: "Polymerization of Acrylonitrile Catalyzed by Thiolate Complexes of Divalent and Trivalent Lanthanoids"Polymer International. 48巻. 502-504 (1999)
[Publications] 真島和志: "1-Aza-1,3-butadiene Complexes of Tantalum : Synthesis and Alkylation of TaCl_2(η^5-C_5Me_5)(1-aza-1,3-butadiene)"Journal of Organometallie Chemistry. 593-594巻. 69-76 (2000)
[Publications] 真島和志: "Novel synthesis of Lanthanoid Complexes starting from Metallic Lanthanoid Sources"Journal of Chemical Society, Dalton Transcation. 3899 (1999)
[Publications] 真島和志: "Catalytic Diversity of Diene Complexes of Niobium and Tantalum on Polymerizations of Ethylene, Norbornene, and Methyl Methacrylate"Macromolecular symposium. (1999)
[Publications] 片岡靖隆: "Third Generation of the Cp'-P Ligand : Highly Stereoselective Control of Central Chirality Arising at a metal Center"Organometallies. 18巻. 5423-5425 (1999)
[Publications] 谷一英: "Activation of E-H(E=hetero atom) and C-H Bonds by Iridium Complexes and Their Application to Homogeneous Catalysis (in Japanese)"有機合成化学協会誌. 57巻. 656-666 (1999)
[Publications] 片岡靖隆: "Direct Observation of Reversible C(sp3)-H Bond Activation. Characterization of the Strauctures of Both Ir Complexes before and after C-H bond activation by Using a Flexible P-N Heterochelate Hybrid Ligand"Organometallics. 18巻. 3563-3565 (1999)
[Publications] 谷一英: "Efficient transfer hydrogenation of alkynes and alkenes with methanol catalyzed by hydrido(methoxo)iridium(III) complexes"Chemical Communications. 1821-1822 (1999)
[Publications] 真島和志: "Unique Complexation of 1,4-Diaza-1,3-butadiene Ligand on Half-metallocene Fragments of Niobium and Tantalum"Organometallics. 18巻. 1471-1481 (1999)
[Publications] 真島和志: "Organometallics Group 3-7"Organometallic Complexes of Niobium and Tantalum. (1999)
[Publications] 真島和志: "Living Polymerization Catalyzed by Transition Metal Complex"Ring-opening Metathesis Polymerization Catalyzed by Tantalum Complexes (in Japanese). 24 (1999)

1999 Fiscal Year Annual Research Report

有機遷移金属錯体の特性に根ざした選択的新反応・新触媒反応の開発

Principal Investigator

谷 一英 大阪大学, 大学院・基礎工学研究科, 教授 (60029444)

Research Products

[Publications] 中山 祐正: "Polymerization of Acrylonitrile Catalyzed by Thiolate Complexes of Divalent and Trivalent Lanthanoids"Polymer International. 48巻. 502-504 (1999)

[Publications] 真島 和志: "1-Aza-1,3-butadiene Complexes of Tantalum : Synthesis and Alkylation of TaCl_2(η^5-C_5Me_5)(1-aza-1,3-butadiene)"Journal of Organometallie Chemistry. 593-594巻. 69-76 (2000)

[Publications] 真島 和志: "Novel synthesis of Lanthanoid Complexes starting from Metallic Lanthanoid Sources"Journal of Chemical Society, Dalton Transcation. 3899 (1999)

[Publications] 真島 和志: "Catalytic Diversity of Diene Complexes of Niobium and Tantalum on Polymerizations of Ethylene, Norbornene, and Methyl Methacrylate"Macromolecular symposium. (1999)

[Publications] 片岡 靖隆: "Third Generation of the Cp'-P Ligand : Highly Stereoselective Control of Central Chirality Arising at a metal Center"Organometallies. 18巻. 5423-5425 (1999)

[Publications] 谷 一英: "Activation of E-H(E=hetero atom) and C-H Bonds by Iridium Complexes and Their Application to Homogeneous Catalysis (in Japanese)"有機合成化学協会誌. 57巻. 656-666 (1999)

[Publications] 片岡 靖隆: "Direct Observation of Reversible C(sp3)-H Bond Activation. Characterization of the Strauctures of Both Ir Complexes before and after C-H bond activation by Using a Flexible P-N Heterochelate Hybrid Ligand"Organometallics. 18巻. 3563-3565 (1999)

[Publications] 谷 一英: "Efficient transfer hydrogenation of alkynes and alkenes with methanol catalyzed by hydrido(methoxo)iridium(III) complexes"Chemical Communications. 1821-1822 (1999)

[Publications] 真島 和志: "Unique Complexation of 1,4-Diaza-1,3-butadiene Ligand on Half-metallocene Fragments of Niobium and Tantalum"Organometallics. 18巻. 1471-1481 (1999)

[Publications] 真島 和志: "Organometallics Group 3-7"Organometallic Complexes of Niobium and Tantalum. (1999)

[Publications] 真島 和志: "Living Polymerization Catalyzed by Transition Metal Complex"Ring-opening Metathesis Polymerization Catalyzed by Tantalum Complexes (in Japanese). 24 (1999)

谷一英大阪大学, 大学院・基礎工学研究科, 教授 (60029444)

[Publications] 中山祐正: "Polymerization of Acrylonitrile Catalyzed by Thiolate Complexes of Divalent and Trivalent Lanthanoids"Polymer International. 48巻. 502-504 (1999)

[Publications] 真島和志: "1-Aza-1,3-butadiene Complexes of Tantalum : Synthesis and Alkylation of TaCl_2(η^5-C_5Me_5)(1-aza-1,3-butadiene)"Journal of Organometallie Chemistry. 593-594巻. 69-76 (2000)

[Publications] 真島和志: "Novel synthesis of Lanthanoid Complexes starting from Metallic Lanthanoid Sources"Journal of Chemical Society, Dalton Transcation. 3899 (1999)

[Publications] 真島和志: "Catalytic Diversity of Diene Complexes of Niobium and Tantalum on Polymerizations of Ethylene, Norbornene, and Methyl Methacrylate"Macromolecular symposium. (1999)

[Publications] 片岡靖隆: "Third Generation of the Cp'-P Ligand : Highly Stereoselective Control of Central Chirality Arising at a metal Center"Organometallies. 18巻. 5423-5425 (1999)

[Publications] 谷一英: "Activation of E-H(E=hetero atom) and C-H Bonds by Iridium Complexes and Their Application to Homogeneous Catalysis (in Japanese)"有機合成化学協会誌. 57巻. 656-666 (1999)

[Publications] 片岡靖隆: "Direct Observation of Reversible C(sp3)-H Bond Activation. Characterization of the Strauctures of Both Ir Complexes before and after C-H bond activation by Using a Flexible P-N Heterochelate Hybrid Ligand"Organometallics. 18巻. 3563-3565 (1999)

[Publications] 谷一英: "Efficient transfer hydrogenation of alkynes and alkenes with methanol catalyzed by hydrido(methoxo)iridium(III) complexes"Chemical Communications. 1821-1822 (1999)

[Publications] 真島和志: "Unique Complexation of 1,4-Diaza-1,3-butadiene Ligand on Half-metallocene Fragments of Niobium and Tantalum"Organometallics. 18巻. 1471-1481 (1999)

[Publications] 真島和志: "Organometallics Group 3-7"Organometallic Complexes of Niobium and Tantalum. (1999)

[Publications] 真島和志: "Living Polymerization Catalyzed by Transition Metal Complex"Ring-opening Metathesis Polymerization Catalyzed by Tantalum Complexes (in Japanese). 24 (1999)