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一种单体(三甲基硅基)甲基锂配合物:合成、结构、分解及初步反应性研究。

A monomeric (trimethylsilyl)methyl lithium complex: synthesis, structure, decomposition and preliminary reactivity studies.

作者信息

Davison Nathan, Waddell Paul G, Dixon Casey, Wills Corinne, Penfold Thomas J, Lu Erli

机构信息

Chemistry-School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK.

出版信息

Dalton Trans. 2022 Jul 19;51(28):10707-10713. doi: 10.1039/d1dt03532k.

Abstract

Monomeric organolithium (LiR) complexes could provide enhanced Li-C bond reactivity and suggest mechanisms for a plethora of LiR-mediated reactions. They are highly sought-after but remain a synthetic challenge for organometallic chemists. In this work, we report the synthesis and characterisation of a monomeric (trimethylsilyl)methyl lithium complex, namely [Li(CHSiMe)(κ-,',''-MeTren)] (1), where MeTren is a tetradentate neutral amine ligand. The structure of 1 was comprehensively examined by single-crystal X-ray diffraction, variable temperature NMR spectroscopy and electron absorption spectroscopy. Complex 1 decomposes ligand C-H and C-N activations to produce a Li amide complex 2. Preliminary reactivity studies of 1 reveal CO insertion and C-H activation reaction patterns.

摘要

单体有机锂(LiR)配合物可以增强Li-C键的反应活性,并为大量LiR介导的反应提供反应机理。它们备受追捧,但对于有机金属化学家来说仍然是一个合成挑战。在这项工作中,我们报道了一种单体(三甲基硅基)甲基锂配合物,即[Li(CHSiMe)(κ-,',''-MeTren)](1)的合成与表征,其中MeTren是一种四齿中性胺配体。通过单晶X射线衍射、变温核磁共振光谱和电子吸收光谱对1的结构进行了全面研究。配合物1通过配体C-H和C-N活化分解生成锂酰胺配合物2。对1的初步反应性研究揭示了CO插入和C-H活化反应模式。

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