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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Oxidative addition of cyanogen bromide to C,N-chelated and Lappert's stannylenes
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Oxidative addition of cyanogen bromide to C,N-chelated and Lappert's stannylenes

机译:氧化氰基溴化物加入C,n-Chelated和Lappert的亚胺

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摘要

Stannylenes of L2Sn type bearing either C,N-chelating (1, L = L-CN = 2-(N,N-dimethylaminomethyl)phenyl) or bulky amido (2, L = L-N = N(SiMe3)(2)) ligands react with cyanogen bromide (Br-C N) via an oxidative-addition reaction to give monomeric six-coordinate (L-CN)(2)Sn(Br)CN (1a) and four-coordinate (L-N)(2)Sn(Br) CN (2a) stannanes in moderate yields. In solution, both 1a and 2a undergo instantaneous bromido-cyanido ligand redistribution reactions, leading to mixtures containing 1a, (L-CN)(2)SnBr2 (1b) and (L-CN)(2)Sn(CN)(2) (1c) or 2a, (L-N)(2)SnBr2 (2b) and (L-N)(2)Sn(CN)(2) (2c), respectively. The prepared species were characterised by multinuclear NMR spectroscopy in solution (1a-c and 2a-c) and in the solid state (1a-c). The crystal structures of 1a/b/c, 2a/b/c and sole 2b were determined by XRD analyses. DFT calculations and QTAIM analysis were also carried out to corroborate the experimental results.
机译:含有C,N-螯合(1,L=L-CN=2-(N,N-二甲氨基甲基)苯基)或大块氨基(2,L=L-N=N(SiMe3)(2))配体的L2Sn型锡烯通过氧化加成反应与溴化氰(Br-CN)反应,以中等产率生成单体六配位(L-CN)(2)锡(Br)CN(1a)和四配位(L-N)(2)锡(Br)CN(2a)锡。在溶液中,1a和2a都会发生瞬时的溴氰基配位体再分配反应,分别生成含有1a、(L-CN)(2)SnBr2(1b)和(L-CN)(2)Sn(CN)(2)(1c)或2a、(L-N)(2)SnBr2(2b)和(L-N)(2)Sn(CN)(2)(2c)的混合物。通过溶液(1a-c和2a-c)和固态(1a-c)中的多核NMR谱对制备的物种进行了表征。通过XRD分析确定了1a/b/c、2a/b/c和sole 2b的晶体结构。DFT计算和QTAIM分析也证实了实验结果。

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