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