半夹芯式16电子化合物CpCo(S2C2B10H10)与重氮乙酸乙酯及联烯三元反应体系
Reactivity of Half-Sandwich 16 Electron Compound CpCo(S2C2B10H10) with Ethyl Diazoacetate and Allenes
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刘贵锋 南京大学化学化工学院, 配位化学国家重点实验室, 南京 210093;中国林科院林产化学工业研究所, 南京 210042  
燕红 南京大学化学化工学院, 配位化学国家重点实验室, 南京 210093 hyan1965@nju.edu.cn 
摘要: 半夹芯式碳硼烷16e金属有机化合物CpCo(S2C2B10H10)与重氮乙酸乙酯及联烯在室温下反应,生成化合物12。在化合物12中,一分子重氮乙酸乙酯与一分子联烯以头-头方式插入Co-B键之间使碳硼烷B(3)/(6)位发生B-H键活化生成B-C键,另有一分子重氮乙酸乙酯使Co-S断裂形成硫叶立德。分别采用红外、核磁、元素分析、质谱和单晶X射线衍射等表征方法对化合物12进行了结构表征。
关键词: 碳硼烷  联烯  重氮乙酸乙酯  B-H键活化
基金项目: 国家自然科学基金(No.21271102)资助项目。
Abstract: The three-component reactions of the 16 electron half-sandwich complex CpCo(S2C2B10H10) (Cp:cyclopentadienyl) with ethyl diazoacetate (EDA) and terminal allenes at ambient temperature lead to compounds 1 and 2. In 1 and 2, one EDA and one allene are inserted into Co-B bonds in a head-to-head mode making the hydrogen atom of the B(3)-H bond transform into the middle carbon of allene. One EDA molecule is also inserted into a Co-S bond to form a sulfide ylide. The new compounds 1 and 2 were characterized by NMR (1H, 11B, 13C), mass spectra, IR spectroscopy and elemental analysis, and their solid-state structures were further characterized by X-ray structural analysis.
Keywords: carborane  allene  ethyl diazoacetate  B-H activation
投稿时间:2016-12-03 修订日期:2016-12-16
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刘贵锋,燕红.半夹芯式16电子化合物CpCo(S2C2B10H10)与重氮乙酸乙酯及联烯三元反应体系[J].无机化学学报,2017,33(3):487-492.
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