半夹芯式16电子化合物CpCo(S2C2B(10)H(10))与重氮乙酸乙酯及联烯三元反应体系  

Reactivity of Half-Sandwich 16 Electron Compound Cp Co(S_2C_2B_(10)H_(10)) with Ethyl Diazoacetate and Allenes

作　　者：刘贵锋[1,2] 燕红[1] LIU Gui-Feng YAN Hong(State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China)

机构地区：[1]南京大学化学化工学院,配位化学国家重点实验室,南京210093 [2]中国林科院林产化学工业研究所,南京210042

出　　处：《无机化学学报》2017年第3期487-492,共6页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21271102)资助项目

摘　　要：半夹芯式碳硼烷16e金属有机化合物Cp Co(S2C2B10H10)与重氮乙酸乙酯及联烯在室温下反应,生成化合物1和2。在化合物1和2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1和2进行了结构表征。The three-component reactions of the 16 electron half-sandwich complex Cp Co（S2C2B（10）H（10））（Cp：cyclopentadienyl） with ethyl diazoacetate（EDA） and terminal allenes at ambient temperature lead to compounds 1and 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,11 B,13C）,mass spectra, IR spectroscopy and elemental analysis, and their solid-state structures were further characterized by X-ray structural analysis.

关 键 词：碳硼烷 联烯 重氮乙酸乙酯 B-H键活化 

分 类 号：O614.812[理学—无机化学]