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 

机构地区：[1]Faculty of Chemistry, Southwest Forestry University, Kunming 650224, China [2]Department of Biology, Honghe University, Menzi 661100, China [3]Department of Chemistry, Yunnan University, Kunming 650091, China

出　　处：《Chinese Chemical Letters》2008年第7期881-884,共4页中国化学快报（英文版）

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

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.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.

关 键 词：Copper and gold Alkyl halide HBr elimination 

分 类 号：O658[理学—分析化学]