N-Heterocyclic Carbenes with a Nido-C_(2)B_(9) Carborane Backbone  

作　　者：Zhongzheng Cui Beining Wang Junxia Li Ronglin Pang Yanrui Kang Xu-Qiong Xiao 

机构地区：[1]Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,College of Material,Chemistry and Chemical Engineering,Hangzhou Normal University,No.2318 Yu hangtong Rd.,Hangzhou,Zhejiang 311121,China

出　　处：《Chinese Journal of Chemistry》2021年第9期2410-2416,共7页中国化学（英文版）

基　　金：support from the National Natural Science Foundation of China(Grant No.21771048);the Natural Science Foundation of Zhejiang Provinee(Grant No.LY17B010002).

摘　　要：The steric and electronic properties of A/-heterocyclic carbenes(NHCs)can be modified by the exocyclic substituents at the nitrogen atoms,by 1-3 atoms'replacements of the five-membered imidazolium skeleton and by the changes of the backbones.Herein,we report the usage of nido-C_(2)B_(3) carbora ne anions as the backb ones of NHCs.Stirring the mixture of sec on dary amino o-carbora nes(lb-le),triethyl orthoformate and HBF4-Et2O results in the unexpected cage-opening of o-carboranes to afford the n/do-C_(2)B_(9) carbora ne anions supported A/-heterocyclic carbene precursors(4b-4e).Deprotonation of 4b with sodium hexamethyldisilazide at-78℃ affords the/V-heterocyclic carbene ligand,which was used to form an Au(I)NHC complex(5).DFT calculations revealed a high-lying lone pair orbitals of the carbene ligands,predicting their strong o-donating abilities.

关 键 词：CARBORANES nido-Carborane anion Carbene ligands Density functional calculations Gold 

分 类 号：O62[理学—有机化学]