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）使用钨作为中央金属，供体桥的双（silylene）络合物，外部供体稳定的甲硅烷基（Silylene）络合物，二聚体（Sillen）络合物（silylene）络合物，其中羰基配体的氧原子在其中相互融合，形成了质量型浓度，以形成质量八的肌烯，并形成了八型剂量的均匀的（8membere）。通过羰基复合物的光解来合成。这些复合物的结构已通过X射线晶体学确定。证明了1,3个取代基的迁移是在孤立的甲硅烷基（甲硅烷基）复合物上发生的。（2）研究了双（silylene）氟苯子配合物的反应性，并基于其对酒精和水的高反应性和甲基二键键的反应性，证明了甲硅烷基配体的高电力性。发现二甲基二甲二甲二甲二甲二甲二甲二甲硅烷基于（甲硅烷基）ruthenium和铁配合物，使二乙酰基（甲硅烷基）配合物。（3）通过具有（磷酸甲基）甲硅烷基体配体的虹膜配合物，我们发现了以下新反应；通过从甲基（Hydrido）的虹膜复合物转移甲基（ME）H2形成Sir（ME）H2的取代基的重新分布，形成了Hydrido（Silylene）复合物，通过1,2-氢化基因从水解中心固定的金属中心等（4）donore的金属中心等（4），以氢化（silylene）复合物形成（hydrido（silylene）复合物）（4） 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与一个silyl群体结合。给出甲基硅烷，并与产生酰基复合物的试验二磷酸盐反应。

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)