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＋, b...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.展开更多
基金the National Natural Science Foundation of China (No.20563005)the Science Foundation of Southwest Forestry University (No.200612M).
文摘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.
