Synthesis of Stable Silylene and Germylene Complexes and the Mechanistic Studies on Catalytic Reactions Utilizing Them

稳定的亚硅基和亚甲锗烷基配合物的合成及其催化反应机理研究

• 批准号: 09440223
• 负责人: OGINO Hiroshi
• 金额: $ 8.38万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440223/
• 关键词: SILYLENE COMPLEX; SILYL (SILYLENE) COMPLEX; BIS (SILYLENE) COMPLEX; GERMYLENE COMPLEX; 1,3-MIGRATION; CATALYTIC REACTION; REDISTRIBUTION REACTION; METHYLATION; シリリン錯体

(1) Using tungsten as a central metal, donor-bridged bis(silylene) complexes, external donor-stabilized silyl(silylene) complexes, dimeric silyl(silylene) complexes in which the oxygen atoms of carbonyl ligands are mutually coordinated to the silylene ligands to form an eight-membered ring, and donor-free germyl(germylene) complexes were synthesized by photolysis of carbonyl complexes. The structures of these complexes have been determined by X-ray crystallography. 1,3-Migration of substituents was demonstrated to occur on isolated silyl(silylene) complexes.(2) Reactivity of bis(silylene)ruthenium complexes was studied, and high electrophilicity of silylene ligands was proved based on their high reactivity toward alcohols and water, and the intramolecular C-H bond activation by the Si-Ru double bond. Dimethylsilylene was found to add to bis(silylene)ruthenium and iron complexes to give disilanyl(silylene) complexes.(3) By means of iridium complexes having a (phosphinoethyl)silyl ligand, we found the following new reactions ; redistribution of substituents on hydrodisilanes, formation of SiR(Me)H2 by transfer of a methyl group from a methyl(hydrido)iridium complex to RSiH3, formation of a hydrido(silylene) complex via 1,2-hydrogen sift from a hydrosilyl ligand to a coordinatively unsaturated metal center, etc.(4) We newly prepared some donor-stabilized cationic germylene complexes and diiron and iron-tungsten complexes bridged by a secondary alkyl-substituted silylene ligand.(5) The first 1 , 2-phenylenedioxysilyl iron complex was synthesized, the structure determined, and the reactivity investigated.(6) As the new reactions of silyl(carbonyl)iron complexes, we found the reaction with LiAlH_4 leading the reduction of a CO ligand and coupling with a silyl group. to give a methylsilane, and the reaction with trialkylphosphites giving acyl complexes.

(1)以钨为中心金属，供体桥联双(亚硅基)配合物、外供体稳定的硅基(亚硅基)配合物、羰基配体的氧原子与亚硅基配体相互配位的二聚硅基(亚硅基)配合物形成八元环，并通过羰基配合物的光解合成了无供体甲锗烷基（甲锗烷基）配合物。这些配合物的结构已通过X射线晶体学确定。孤立的硅基(亚硅基)配合物上被证明会发生1,3-取代基的迁移。(2)研究了双(亚硅基)钌配合物的反应性,并基于其对醇和水的高反应性证明了亚硅基配体的高亲电性，以及Si-Ru双键对分子内C-H键的活化。发现二甲基亚硅基与双(亚甲硅基)钌和铁配合物加成得到二硅烷基(亚硅基)配合物。(3)通过具有(膦乙基)甲硅烷基配体的铱配合物，我们发现了以下新反应；氢化二硅烷上取代基的重新分配，通过将甲基从甲基（氢化）铱络合物转移到 RSiH3 形成 SiR（Me）H2，通过 1,2-氢筛从氢化硅烷基配体形成氢化（亚硅基）络合物(4)我们新制备了一些供体稳定的阳离子甲亚甲基配合物以及二铁和(5)合成了第一个1,2-亚苯基二氧基甲硅烷基铁配合物，确定了结构，并考察了反应活性。(6)作为甲硅烷基(羰基)的新反应铁络合物中，我们发现与 LiAlH_4 的反应导致 CO 配体还原并与甲硅烷基偶联。得到甲基硅烷，与亚磷酸三烷基酯反应得到酰基络合物。

项目成果

Hiroaki Wada: "Fluxional behavior of alkoxy-bridged bis(silylene)ruthenium complexes caused by rota-tion of the silylene ligands" Chem.Lett.1988. 993-994 (1998)

Hiroaki Wada：“由亚硅基配体旋转引起的烷氧基桥联双（亚硅基）钌络合物的流动行为”Chem.Lett.1988。

Keiji Ueno: "Synthesis, structure, and fluxional behavior of base-stabilized silyl(silylene)tungsten com-plexes" Organometallics. 17. 2138-2140 (1998)

Keiji Ueno：“碱稳定的硅基（亚硅基）钨配合物的合成、结构和流动行为”有机金属。

Masaaki Okazaki: "Generation of a hydrido(silylene)iridium(I)species via the reductive elimination of alkane and 1,2-H-shift from the silicon atom to the Ir(I)metal center" J.Organomet.Chem.553. 1-13 (1998)

Masaaki Okazaki：“通过烷烃的还原消除和从硅原子到 Ir(I) 金属中心的 1,2-H 转移生成氢化(亚硅基)铱 (I) 物种”J.Organomet.Chem.553

Hiromi Tobita: "Synthesis,structure,and reactivity of a bis(silylene)(carbonyl)ruhenium complex and a novel addition reaction of photochemically generated dimethylsilylene to bis(silylene)complexes" Organometallics. 17. 2844-2849 (1998)

Hiromi Tobita：“双（亚硅基）（羰基）钌络合物的合成、结构和反应性以及光化学生成的二甲基亚硅基到双（亚硅基）络合物的新型加成反应”有机金属。

Hiroaki Wada, Hiromi Tobita, and Hiroshi Ogino: "Fluxional behavior of alkoxy-bridged bis (silylene) ruthenium complexes Cp^* (Me_3P) Ru [SiMe_2・・・O (R) ・・・SiMe_2] (R=Me, ^tBu) caused by rotation of the silylene ligands" Chem.Lett.1998. 993-994 (1998)

Hiroaki Wada、Hiromi Tobita 和 Hiroshi Ogino：“烷氧基桥联双（亚硅基）钌络合物 Cp^* (Me_3P) Ru [SiMe_2・・・O (R) ・・・SiMe_2] (R=Me, ^) 的通量行为tBu) 由亚硅基配体的旋转引起”Chem.Lett.1998. 993-994 (1998)