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

近年来，硅烯、硅烯和二硅烯等不饱和有机化合物的过渡金属配合物的制备一直是人们关注的焦点。作为三亚甲基烯过渡金属配合物的硅类似物，我们研究了通过小环有机硅化合物与金属羰基反应制备eta4-硅三亚甲基甲烷配合物(III，IV R=MES)的方法。已发表了关于硅化合物的全文，并尝试制备其锗类似物。然而，由于产率较低，其吸湿性不稳定，导致相应的小环有机锗化合物(V.R=MES)的分离。另一方面，引入更多的大基团(V，R=DIS)使其分离成为可能，但它干扰了与金属羰基的反应。通过这些研究，首次实现了稳定的小环有机锗化合物的分离。在今后的小环有机锗和锡化合物的合成策略中，应从使用二价物种的C-Ge(Sn)Bonf形成转变为C-C键的形成，如双炔基锗和锡烷的二炔偶联。

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.