Synthesis of Transition metal conplexes of Unsaturated Silicon, Germanium and Tin Compounds

不饱和硅、锗、锡化合物过渡金属配合物的合成

• 批准号: 05640591
• 负责人: KABE Yoshio
• 金额: $ 1.09万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05640591/
• 关键词: Silicon; Silatrimethylenemethane; Germirane; Three-membered ring; Trnaistion metal complexes; ゲルマニウム; スズ

Recently much interest continue to focuss on the preparation of transition-metal complexes of unsaturated silicon compounds such as silylenes, silenes and disilenes.As silicon-analogue of trimethylenemetahne transition-metal complexes, we investigated the preparation of eta4-silatrimethylenemethane complexes (III,IV R=Mes) by reactions of small ring organosilicon compounds with metal carbonyls.Full manuscript on silicon compounds was published and preparation of their germanium-analogue was attempted.However low yield and its hygroscopic instability preculude isolation of the corresponding small ring organogermanium compound(V.R=Mes).On the other hand, introduction of more bulky groups (V,R=Dis) made its isolation possible but it disturbed the reaction with metal carbonyls. From these studies, first isolation of stable small ring organogermanium compounds was achieved. In futhre synthetic strategy for small ring organogermanium and tin compounds should be changed from C-Ge (Sn) bonf formation using divalent species, to C-Cbond formation such as diyne coupling of bisalkynylgermane and stannane.

近年来，不饱和硅化合物（如硅烯、硅烯和二硅烯）的过渡金属配合物的制备一直是人们关注的焦点，作为三亚甲基甲烷过渡金属配合物的硅类似物，我们研究了η 4-硅三亚甲基甲烷配合物的制备（三）IV R=Mes）通过小环有机硅化合物与金属羰基化合物的反应，本文报道了一种新的有机锗类似物的合成方法，但收率低，吸湿不稳定，不利于合成相应的小环有机锗化合物（V，R=Mes），另一方面，引入体积较大的基团（V，R=Dis）使其分离成为可能，但干扰了与金属羰基化合物的反应。从这些研究中，第一个稳定的小环有机锗化合物的分离实现。今后小环有机锗锡化合物的合成策略应从二价物种的C-Ge（Sn）键形成转变为C-C键形成，如双炔基锗烷与锡烷的二炔偶联。

项目成果

W.Ando,H.Ohgaki,Y.Kabe: "Stable Germirane Derivatives" Angew.Chem.Int.Ed.Engl.33. 659-661 (1994)

W.Ando、H.Ohgaki、Y.Kabe：“稳定的 Germirane 衍生物”Angew.Chem.Int.Ed.Engl.33。

Yoshio Kabe, Takao Yamamoto, Wataru Ando: "Synthesis and Properties of eta4-Silatrimethylenemethane-Iron and Ruthenium-Complexes" Organometallics. 13. 4606-4615 (1994)

Yoshio Kabe、Takao Yamamoto、Wataru Ando：“eta4-硅杂三亚甲基甲烷-铁和钌复合物的合成和性能”有机金属。

Y.Kabe,T.Yamamoto,W,Ando: "Synthesis and Properties of n4-Silatrimethylenemetbane Iron and Ruthenivm-Complexes" Organometallics. 13. 4606-4615 (1994)

Y.Kabe，T.Yamamoto，W，Ando：“n4-Silatrimmethylmetbane 铁和 Ruthenivm 配合物的合成和性能”有机金属。

W.Ando,H.Ohgaki,Y.Kabe: "Stable Germirane Derivatives" Angew.Chem.Int.Ed.Engl.33. (1994)

W.Ando、H.Ohgaki、Y.Kabe：“稳定的 Germirane 衍生物”Angew.Chem.Int.Ed.Engl.33。

Yoshio Kabe,Takao Yamamoto,Wataru Ando: "Synthesis and Properties of η4-Silatrimethylenemethane-Iron and Ruthenium-Complexes" Organometallics. 13. 4606-4615 (1994)

Yoshio Kabe、Takao Yamamoto、Wataru Ando：“η4-硅杂三亚甲基甲烷-铁和钌复合物的合成和性质”有机金属学 13. 4606-4615 (1994)。