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采用密度泛函理论B3LYP方法在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方法确认了中间体和过渡态.又用QCISD(T)/6-311++G**//B3LYP/6-311++G**方法计算了各个驻点的单点能,计算结果表明单重态的硅烯与异硫氰酸的反应有抽提硫、插入、抽提亚氨基的路径.而经由三元环中间体的抽提硫反应SiH2+HNCS→IM1→TS2→IM3→TS3→IM4→SiH2S+HNC(P1),反应能垒最低,为主反应通道,硫代硅甲醛和异氰氢酸为主产物.硅烯直接抽提硫、插入N-H键和经由三元环中间体的亚氨基抽提反应为竞争反应通道,在室温下可以发生,应为次反应通道.
The total geometric parameters of the reactants, intermediates and transition states were optimized by density functional theory B3LYP method at B3LYP / 6-311 ++ G ** level. Intermediates and transition states were confirmed by frequency analysis and IRC. The single point energy of each stagnation point was calculated by QCISD (T) / 6-311 ++ G ** / B3LYP / 6-311 ++ G ** method. The calculated results show that the singlet energy The reaction of cyanic acid has the following steps: extraction of sulfur, insertion and extraction of imino groups, SiH2 + HNCS → IM1 → TS2 → IM3 → TS3 → IM4 → SiH2S + HNC (P1) , The lowest reaction energy barrier, the main reaction channel, the main products of thiosilicate formaldehyde and isocyanic acid.Silicone direct extraction of sulfur, insert NH bond and through the three-membered ring intermediate imino extraction reaction for the competitive reaction Channels, which can occur at room temperature, should be secondary channels.