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采用密度泛函理论B3LYP方法研究了单、三重态CCl_2与HNCO的反应机理,在B3LYP/6-311++G~(**)水平上对反应物,中间体,过渡态进行了全几何参数优化,通过频率分析和IRC确定中间体和过渡态,并用G3方法计算了各个驻点的单点能.计算结果表明:单重态的CCl_2与HNCO的反应有抽提氧、插入N-H键、抽提亚氨基的路径,三重态的CCl_2与HNCO发生抽提氢的反应,其中单重态反应通道HNCO+CCl_2→IM3→TS2→P2(C_2Cl_2ONH)反应能垒最低,为主反应通道.
The reaction mechanism of single and triplet CCl 2 with HNCO was studied by density functional theory (B3LYP) method. The geometries of reactants, intermediates and transition states were investigated at B3LYP / 6-311 ++ G ~ (**) Optimization, the intermediates and transition states were determined by frequency analysis and IRC, and the single point energy of each stagnation point was calculated by G3 method.The calculated results show that the reaction of singlet state CCl_2 with HNCO has extraction of oxygen, insertion of NH bond, pumping In the pathways of trimethylenes, CCl_2 and HNCO in the triplet state undergo hydrogen extraction. The HNCO + CCl_2 → IM3 → TS2 → P2 (C_2Cl_2ONH) reaction has the lowest energy barrier and is the main reaction channel.