The cycloaddition reaction of ethylene and methane mediated by Ir^(+) to generate a half-sandwich structure Ir HCp^(+)  

作　　者：Wei Li Hechen Wu Xunlei Ding Xiaonan Wu 

机构地区：[1]School of Mathematics and Physics,North China Electric Power University,Beijing 102206,China [2]Department of Chemistry,Fudan University,Shanghai 200433,China [3]Institute of Clusters and Low Dimensional Nanomaterials,North China Electric Power University,Beijing 102206,China

出　　处：《Chinese Chemical Letters》2023年第1期192-197,共6页中国化学快报（英文版）

基　　金：supported by Beijing Natural Science Foundation(No.2214064);the National Natural Science Foundation of China(Nos.21603037,21688102,92161115,21973016,91545122);the Fundamental Research Funds for the Central Universities(Nos.JB2015RCY03,JB2019MS052)supported by the fund of North China Electric Power University。

摘　　要：The cycloaddition reactions of methane and ethylene mediated by Ir^(+) have been designed and studied by the techniques of mass spectrometry in conjunction with theoretical calculations.Studies have shown that Ir^(+) can mediate the cycloaddition reaction of CH4and two C_(2)H_(4) to generate a half-sandwich structure IrHCp^(+)(Cp=η^(5)-C_(5)H_(5))including pentamethylcyclopentadienyl ligand by continuous dehydrogenation reaction with the forming of three C-C bonds and seven C-H bonds.The orbital analysis indicates the mechanism of the cyclization reaction to generation of pentamethylcyclopentadienyl ligand with odd number carbon atom depends on the overlap ofπorbitals in-C_(2)H_(2) and carbene,which is more difficult than the forming of cyclobutadiene ligand and benzene.This study may help to understand the reaction mechanism in the cycloaddition reactions of organic compounds,which will be useful to guide the rational design of new catalysts with tailored selectivity and increased efficiency.

关 键 词：Cycloaddition reaction Mass spectrometry Theoretical calculation Half-sandwich structure 

分 类 号：O657.63[理学—分析化学]