Elimination of HBr from CH_3Br by Cu^+ and Au^+:A DFT study

作     者：Tao Hong Li Chuan Ming Wang Xiang Yi Liu Xiao Guang Xie 

作者机构：Faculty of Chemistry Southwest Forestry University Kunming 650224 China Department of Biology Honghe University Menzi 661100 China Department of Chemistry Yunnan University Kunming 650091 China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2008年第19卷第7期

页      面：881-884页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070302[理学-分析化学] 0703[理学-化学] 

基　　金：the National Natural Science Foundation of China (No.20563005) the Science Foundation of Southwest Forestry University (No.200612M) 

主　　题：Copper and gold Alkyl halide HBr elimination 

摘      要：The elimination of HBr from CH3Br by ground state of Cu＋ and Au＋ has been investigated by using DFT methods. A mechanism of one-step HBr elimination leading to CuCH2＋ was identified. For the formation of AuCH2＋, besides the one-step mechanism, another two-step HBr elimination pathway through a C-Br bond insertion intermediate was also found, and this pathway is energetically more favorable than the one-step mechanism. The calculated reaction energy barriers show that the formation of AuCH2＋ is energetically much more favorable than the formation of CuCH2＋. The experimental observations are well explained.