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一种具有铁氢键和锗氢键的铁二亚甲基络合物:合成、结构及反应活性

An iron germylene complex having Fe-H and Ge-H bonds: synthesis, structure and reactivity.

作者信息

Dhungana Tara Prasad, Hashimoto Hisako, Tobita Hiromi

机构信息

Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.

出版信息

Dalton Trans. 2017 Jun 27;46(25):8167-8179. doi: 10.1039/c7dt01159h.

Abstract

A base-free iron germylene complex Cp*(CO)(H)Fe[double bond, length as m-dash]GeH{C(SiMe)} (1) was synthesised by abstraction of pyridine from a germyl complex Cp*(CO)(py)FeGeH{C(SiMe)} (2), which was prepared by treatment of Cp*Fe(CO)(py)(Me) with HGeC(SiMe). X-ray crystallographic analysis revealed that 1 has an Fe-Ge bond that is the shortest among those ever reported. Reactivity of 1 toward several polar unsaturated organic compounds was investigated. Complex 1 underwent stoichiometric hydrogermylation of carbonyl compounds such as ketones, aldehydes and isocyanates (RNCO) at room temperature. In contrast, the reactions of 1 with isothiocyanates (RNCS) resulted in clean cleavage of the C[double bond, length as m-dash]S double bonds.

摘要

通过从锗基配合物Cp*(CO)(py)FeGeH{C(SiMe)} (2)中脱去吡啶合成了一种无碱铁二亚锗烯配合物Cp*(CO)(H)Fe═GeH{C(SiMe)} (1),配合物2是通过用HGeC(SiMe)处理Cp*Fe(CO)(py)(Me)制备的。X射线晶体学分析表明,1中的Fe-Ge键是迄今报道的最短的。研究了1对几种极性不饱和有机化合物的反应活性。配合物1在室温下对羰基化合物如酮、醛和异氰酸酯(RNCO)进行化学计量的氢锗化反应。相比之下,1与异硫氰酸酯(RNCS)的反应导致C═S双键的完全断裂。

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