Charman Rex S C, Mahon Mary F, Lowe John P, Liptrot David J
Department of Chemistry, University of Bath. Claverton Down, Bath, BA2 7AY UK.
Dalton Trans. 2022 Jan 17;51(3):831-835. doi: 10.1039/d1dt03109k.
Three ring-expanded N-heterocyclic carbene-supported copper(I) triphenylstannyls have been synthesised by the reaction of (RE-NHC)CuOBu with triphenylstannane (RE-NHC = 6-Mes, 6-Dipp, 7-Dipp). The compounds were characterised by NMR spectroscopy and X-ray crystallography. Reaction of (6-Mes)CuSnPh with di--tolyl carbodiimide, phenyl isocyanate and phenylisothiocyanate gives access to a copper(I) benzamidinate, benzamide and benzothiamide respectively phenyl transfer from the triphenylstannyl anion with concomitant formation of (PhSn). Attempts to exploit this reactivity under a catalytic regime were hindered by rapid copper(I)-catalysed dismutation of PhSnH to PhSn, various perphenylated tin oligomers, H and a metallic material thought to be Sn(0). Mechanistic insight was provided by reaction monitoring NMR spectroscopy and mass spectrometry.
通过（RE-NHC）CuOBu与三苯基锡烷反应（RE-NHC = 6-Mes、6-Dipp、7-Dipp）合成了三种扩环N-杂环卡宾支撑的铜（I）三苯基锡化合物。通过核磁共振光谱和X射线晶体学对这些化合物进行了表征。（6-Mes）CuSnPh与二对甲苯基碳二亚胺、苯基异氰酸酯和苯基异硫氰酸酯反应分别得到一种铜（I）苯甲脒、苯甲酰胺和苯硫酰胺，三苯基锡阴离子发生苯基转移并伴随生成（PhSn）。在催化体系下利用这种反应活性的尝试受到了PhSnH快速发生铜（I）催化歧化生成PhSn、各种全苯基化锡低聚物、H以及一种被认为是Sn（0）的金属材料的阻碍。通过反应监测——核磁共振光谱和质谱提供了机理见解。
