1998 Fiscal Year Annual Research Report

典型元素-遷移金属間結合の化学

Research Project

Project/Area Number	09239105
Research Category	Grant-in-Aid for Scientific Research on Priority Areas (A)
Research Institution	Osaka City University
Principal Investigator	小澤文幸大阪市立大学, 工学部, 教授 (40134837)
Co-Investigator(Kenkyū-buntansha)	飛田博実東北大学, 大学院理学研究科, 助教授 (30180160) 宮浦憲夫北海道大学, 大学院工学研究科, 教授 (10002049) 巽和行名古屋大学, 物質科学国際研究センター, 教授 (10155096) 榊茂好熊本大学, 工学部, 教授 (20094013)
Keywords	ジシリル錯体 / シリレン錯体 / ジボリル錯体 / スルフィド錯体 / 金属クラスター / ヒドロシリル化反応 / 酸化的付加反応 / 挿入反応
Research Abstract	[小澤文幸](1)cis-Pt(SiR_3)_2L_2錯体が非平面構造であること、この構造上の歪みがアルキン挿入反応性を支配する重要な因子であることを明らかにした.(2)アルケニルルテニウム錯体とヒドロシランとの反応が2種類の反応機構(σ-結合メタセシスと酸化的付加ー還元的脱離)で進行することを明らかにした. [榊茂好](1)エチレンの白金(0)触媒ヒドロシリル化反応がChalk-Harrod機構で進行すること、律速過程がPt-H結合へエチレン挿入生成物の異性化過程であることを明かにした.(2)白金(0)錯体へのSi-Cσ結合の酸化的付加反応の遷移状態が非平面構造であること、その理由が立体的因子であることを明かにした. [巽和行](1)欠電子性第6族遷移金属錯体に結合したチオラートの炭素-硫黄結合切断反応を見いだし、単核スルフィド錯体を得る独自の合成ルートへと展開した.(2)ポリスルフィド錯体とアルキン類およびハロアルカン類との炭素-硫黄結合生成反応を用いて分子構築を行なった.(3)鉄や銅などを含む異核金属スルフィドクラスターの合成法を確立するとともに、その高次集積化に成功した. [宮浦憲夫](1)遷移金属触媒反応による炭素-炭素不飽和結合に対するジホウ素化合物の付加反応および有機求電子試薬とのクロスカップリング反応を検討し、有機ホウ素化合物の新たな合成法を開発した.(2)有機ボロン酸の合成化学的利用を目的として、ロジウム触媒を用いるα,β-不飽和ケトン、エステルに対するマイケル型付加反応の開発を行った. [飛田博実](1)アルコキシ架橋ビス(シリレン)錯体とジシラニル(シリレン)錯体の相互変換法を見いだした.(2)配位不飽和なヒドロシリルイリジウム錯体とヒドリド(シリレン)錯体が1,2-水素移動を介した速い平衡状態にあることを明らかにした.

Research Products
(15 results)

All Other

All Publications (15 results)

[Publications] 丸山洋一郎: "Reactions of Alkenylruthenium(II)Complexes with Hydrosilane:C-Si vs C-H Bond Formation" Chemistry Letters. (9). 905-906 (1998)
[Publications] 片山博之: "Convenient Routes to Vinylideneruthenium Dichlorides with Basic and Bulky Tertiary Phosphine Ligands(PPri_3 and PCy_3)" Organometallics. 17(23). 5190-5196 (1998)
[Publications] 小澤文幸: "Mechanistic Study on the Insertion of Phenylacetylene into cis-Bis(silyl)platinum(II)" Organometallics. 17(26). 5630-5639 (1998)
[Publications] 榊茂好: "A Theoretical Study of the C-H Activation of Methane Derivatives. Significant Effects of Electron-withdrawing Substituents" Organometallics. 17(7). 1278-1289 (1998)
[Publications] 榊茂好: "Theoretical Study of Platinum(0)-Catalyzed Hydrosilylation of Ethylene. Chalk-Harrod Mechanism or Modified Chalk-Harrod Mechanism" Organometallics. 17(12). 2510-2523 (1998)
[Publications] 榊茂好: "Is a Transition State Planar or non-Planar in Oxidative Additions of C-H,Si-H,C-C,and Si-C Bonds to Pt(PH_3)_2 ? A Theoretical Study" Journal of Physical Chemistry. 102(41). 8027-8036 (1998)
[Publications] 川口博之: "Mono(pentamethylcyclopentadienyl)tantalum Complexes Cotaining a Structurally Versatile Enediamido(2-)Ligand" Organometallics. 17(20). 4380-4386 (1998)
[Publications] J.-P.Lang: "Low Temperature Solid State Reactions of(NH_4)_2[MS_4](M=W,Mo) with[Cu(CH_3CN)_4](PF_6)and CuBr in the Presence of Bis(diphenylphosphino)metahne(dppm)" Inorganic Chemistry. 37(24). 6308-6316 (1998)
[Publications] 杉山浩康: "Synthesis of Alkynethiolato and Alkyneselenolato Complexes of Titanocene(IV)and Samarocene(III)" Inorganic Chemistry. 37(26). 6773-6779 (1998)
[Publications] 石山竜生: "Platinum(0)-Catalyzed Diboration of Allenes with Bis(pinacolato)diboron" Tetrahedron Letters. 39. 2357-2360 (1998)
[Publications] 高谷佳輝: "Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl- and 1-Alkenylboronic Acids to Enones" Journal of the American Chemical Society. 120(22). 5579-5580 (1998)
[Publications] 酒井正明: "Rhodium-Catalyzed Addition of Organoboronic Acids to Aldehydes" Angew.Chem.Int.Ed.Engl.37. 3279-3281 (1998)
[Publications] 岡崎雅明: "Thermal Reactions of Alkyl(hydrido)(hydrosilyl)iridium(III)Complexes:Generation of a Hydrido(silylene)iridium(I)Species via the Reductive Elimination" Jounal of Organometallic Chemistry. 553. 1-13 (1998)
[Publications] 飛田博実: "Synthesis,Structure,and Reactivity of a Bis(silylene)(carbonyl)ruthenium Complex and a Novel Addition Reaction of Photochemically Generated Dimethylsilylene to Bis(silylene)Complexes" Orgsnometallics. 17(3). 2844-2849 (1998)
[Publications] 飛田博実: "Synthesis and Properties of Intramolecularly Base-Stabilized Disilanyl(silylene)ruthenium and-iron Complexes" Organometallics. 17(3). 2850-2856 (1998)

1998 Fiscal Year Annual Research Report

典型元素-遷移金属間結合の化学

Principal Investigator

小澤 文幸 大阪市立大学, 工学部, 教授 (40134837)

Research Products

[Publications] 丸山洋一郎: "Reactions of Alkenylruthenium(II)Complexes with Hydrosilane:C-Si vs C-H Bond Formation" Chemistry Letters. (9). 905-906 (1998)

[Publications] 片山博之: "Convenient Routes to Vinylideneruthenium Dichlorides with Basic and Bulky Tertiary Phosphine Ligands(PPri_3 and PCy_3)" Organometallics. 17(23). 5190-5196 (1998)

[Publications] 小澤文幸: "Mechanistic Study on the Insertion of Phenylacetylene into cis-Bis(silyl)platinum(II)" Organometallics. 17(26). 5630-5639 (1998)

[Publications] 榊 茂好: "A Theoretical Study of the C-H Activation of Methane Derivatives. Significant Effects of Electron-withdrawing Substituents" Organometallics. 17(7). 1278-1289 (1998)

[Publications] 榊 茂好: "Theoretical Study of Platinum(0)-Catalyzed Hydrosilylation of Ethylene. Chalk-Harrod Mechanism or Modified Chalk-Harrod Mechanism" Organometallics. 17(12). 2510-2523 (1998)

[Publications] 榊 茂好: "Is a Transition State Planar or non-Planar in Oxidative Additions of C-H,Si-H,C-C,and Si-C Bonds to Pt(PH_3)_2 ? A Theoretical Study" Journal of Physical Chemistry. 102(41). 8027-8036 (1998)

[Publications] 川口博之: "Mono(pentamethylcyclopentadienyl)tantalum Complexes Cotaining a Structurally Versatile Enediamido(2-)Ligand" Organometallics. 17(20). 4380-4386 (1998)

[Publications] J.-P.Lang: "Low Temperature Solid State Reactions of(NH_4)_2[MS_4](M=W,Mo) with[Cu(CH_3CN)_4](PF_6)and CuBr in the Presence of Bis(diphenylphosphino)metahne(dppm)" Inorganic Chemistry. 37(24). 6308-6316 (1998)

[Publications] 杉山浩康: "Synthesis of Alkynethiolato and Alkyneselenolato Complexes of Titanocene(IV)and Samarocene(III)" Inorganic Chemistry. 37(26). 6773-6779 (1998)

[Publications] 石山竜生: "Platinum(0)-Catalyzed Diboration of Allenes with Bis(pinacolato)diboron" Tetrahedron Letters. 39. 2357-2360 (1998)

[Publications] 高谷佳輝: "Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl- and 1-Alkenylboronic Acids to Enones" Journal of the American Chemical Society. 120(22). 5579-5580 (1998)

[Publications] 酒井正明: "Rhodium-Catalyzed Addition of Organoboronic Acids to Aldehydes" Angew.Chem.Int.Ed.Engl.37. 3279-3281 (1998)

[Publications] 岡崎雅明: "Thermal Reactions of Alkyl(hydrido)(hydrosilyl)iridium(III)Complexes:Generation of a Hydrido(silylene)iridium(I)Species via the Reductive Elimination" Jounal of Organometallic Chemistry. 553. 1-13 (1998)

[Publications] 飛田博実: "Synthesis,Structure,and Reactivity of a Bis(silylene)(carbonyl)ruthenium Complex and a Novel Addition Reaction of Photochemically Generated Dimethylsilylene to Bis(silylene)Complexes" Orgsnometallics. 17(3). 2844-2849 (1998)

[Publications] 飛田博実: "Synthesis and Properties of Intramolecularly Base-Stabilized Disilanyl(silylene)ruthenium and-iron Complexes" Organometallics. 17(3). 2850-2856 (1998)

小澤文幸大阪市立大学, 工学部, 教授 (40134837)

[Publications] 榊茂好: "A Theoretical Study of the C-H Activation of Methane Derivatives. Significant Effects of Electron-withdrawing Substituents" Organometallics. 17(7). 1278-1289 (1998)

[Publications] 榊茂好: "Theoretical Study of Platinum(0)-Catalyzed Hydrosilylation of Ethylene. Chalk-Harrod Mechanism or Modified Chalk-Harrod Mechanism" Organometallics. 17(12). 2510-2523 (1998)

[Publications] 榊茂好: "Is a Transition State Planar or non-Planar in Oxidative Additions of C-H,Si-H,C-C,and Si-C Bonds to Pt(PH_3)_2 ? A Theoretical Study" Journal of Physical Chemistry. 102(41). 8027-8036 (1998)