The mechanisms for CH3- and CH_4-elimination in the gas phase reaction of ground-state Zr with 2-butyne has been investigated in detail using B3LYP method.For the elimination of CH3,two mechanisms which are similar to...The mechanisms for CH3- and CH_4-elimination in the gas phase reaction of ground-state Zr with 2-butyne has been investigated in detail using B3LYP method.For the elimination of CH3,two mechanisms which are similar to those previously found for the reactions of Y and Zr with propyne are identified.The mechanism for the elimination of CH_4 was revealed as：Zr ＋ CH3C≡CCH_3→π-complex→TS（H-migration）→HZr-（H2CCC）-CH3→TS（C-C insertion）→（H2CCC）-HZr-CH3→TS（H-migration）→CH4＋ ZrC3H2.展开更多
基金supported by the General Programs of the Applied Basic Research of Science and Technology, Department of Yunnan Province(Nos.2008ZC095 and 2007B066M).
文摘The mechanisms for CH3- and CH_4-elimination in the gas phase reaction of ground-state Zr with 2-butyne has been investigated in detail using B3LYP method.For the elimination of CH3,two mechanisms which are similar to those previously found for the reactions of Y and Zr with propyne are identified.The mechanism for the elimination of CH_4 was revealed as：Zr ＋ CH3C≡CCH_3→π-complex→TS（H-migration）→HZr-（H2CCC）-CH3→TS（C-C insertion）→（H2CCC）-HZr-CH3→TS（H-migration）→CH4＋ ZrC3H2.
