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采用密度泛函理论的B3LYP方法,在6-311++G(d,p)和DGDZVP基组水平上研究了CH3SCH3在Fe+作用下的脱烷基化的四重态和六重态微观反应机理,全参数优化了反应势能面上各驻点的几何构型,振动分析和内禀反应坐标(IRC)分析结果证实了中间体和过渡态的真实性.找到了三条可能的反应通道,对结果的分析表明:对于六重态的反应体系,二甲硫醚的脱甲烷化反应主要经历了四个基本步骤,即先驱复合物、C—S活化、(-H转移和非反应性的分裂.对于四重态的Fe+/CH3SCH3反应体系,含有C—S和C—H插入反应的两个路径都可以导致脱甲烷反应的发生,其中C—S插入反应路径的能垒较低,是主要反应通道.
The density functional theory (B3LYP) method was used to study the dealkylation of CH3SCH3 under the action of Fe + at the level of 6-311 ++ G (d, p) and DGDZVP. , All the parameters optimize the geometrical configuration of each stationary point on the potential surface of potential energy, and the results of vibration analysis and intrinsic reaction coordinate (IRC) confirm the authenticity of intermediates and transition states. Three possible reaction channels were found, The analysis shows that for the six - state reaction system, the demethanization reaction of dimethyl sulfide mainly goes through four basic steps: the precursor complex, C - S activation, (- H transfer and nonreactive cleavage. For the tetrad state Fe + / CH3SCH3 reaction system, both of the C-S and C-H insertion reactions can lead to the demethanization reaction, in which the energy barrier of C-S insertion into the reaction pathway is lower and is the main reaction aisle.