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铜(I)的有机锡化物和有机锗化物的合成、结构及反应活性

Synthesis, Structures, and Reactivity of Organostannanides and Organogermanides of Copper(I).

作者信息

Charman Rex S C, Liptrot David J

机构信息

Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.

出版信息

Chempluschem. 2024 Dec;89(12):e202400439. doi: 10.1002/cplu.202400439. Epub 2024 Oct 18.

Abstract

Organogermane and organostannane compounds are valuable reagents in cross coupling reactions, and copper(I) germanide and stannanide complexes can provide convenient access to these compounds. This review presents the chemistry of copper(I) germanide and stannanide complexes, with a particular focus on systems at the frontier of organic and inorganic chemistry where structural characterisation of coordination complexes facilitates rationalisation of organic mechanisms. These species show both similarities to, and significant divergences from their lighter silanide congeners. For example, they are all viable sources of the relevant organotetranide anion, but in the cases of both germanium and tin, the tetranides can be accessed via direct deprotonation of the corresponding tetranes, a reaction unknown for silicon. Further divergences between copper(I) germanides and stannanides are highlighted; whilst both can be used in productive organic transformations to access organotetranes, catalytic reactions are only reported for germanium. The rather striking ability of triphenylstannanides to acts as sources of the phenyl anion are discussed; the mechanism of this reaction is still subject to discussion, but its absence in the chemistry of germanium and silicon is now well-rationalised. We conclude this review by considering potential research directions in the synthesis and exploitation of copper(I) germanides and stannanides.

摘要

有机锗烷和有机锡烷化合物是交叉偶联反应中有价值的试剂,而一价铜的锗化物和锡化物配合物能够方便地制备这些化合物。本综述介绍了一价铜的锗化物和锡化物配合物的化学性质,特别关注有机化学和无机化学前沿的体系,在这些体系中,配位配合物的结构表征有助于合理阐释有机反应机理。这些物种与其较轻的硅化物同系物既有相似之处,也有显著差异。例如,它们都是相应有机四价阴离子的可行来源,但对于锗和锡的情况,四价阴离子可以通过相应四氢化物的直接去质子化得到,而硅的这种反应并不为人所知。一价铜的锗化物和锡化物之间的进一步差异也得到了强调;虽然它们都可用于有效的有机转化以制备有机四氢化物,但仅报道了锗的催化反应。文中讨论了三苯基锡化物作为苯基阴离子来源的相当显著的能力;该反应的机理仍在讨论中,但现在已经很好地解释了它在锗和硅化学中的不存在。我们通过考虑一价铜的锗化物和锡化物的合成与应用方面的潜在研究方向来结束本综述。

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