Hydrolysis of an organophosphorus pesticide: a computational reaction study on triazophos
Hydrolysis of an organophosphorus pesticide: a computational reaction study on triazophos
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DOI：
10.1007/s00214-022-02925-2
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发表时间：
2022-10
影响因子：
1.7
通讯作者：
Rong Chen;Xiaoling Luo;Guoming Liang
中科院分区：
文献类型：
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作者：
Rong Chen;Xiaoling Luo;Guoming Liang
通过B3LYP/6-311++G(d,p), M06-2X/6-311++G（d,p）以及MP2/6-311G(d)水平，系统地研究了三唑磷的可选水解通道。两种可能的机制，P-OR1和P-OEt的分解途径，进行了深入的研究；同时，对协调和逐步中性路径进行了详细的讨论。为了探讨额外水的影响，对额外水存在下的水解通道进行了详细的研究。采用PCM模型，采用M06-2X/6-311+G（d,p）法评价了溶剂对水的影响。我们的结果令人信服地表明，阶梯式过程比协同过程更有利，最优选的机制似乎是P-OR1断裂通道的阶梯式直接水解。水催化水解在能量上优于直接水解。此外，溶剂效应对反应机理的影响很小。
The alternative hydrolysis channels for triazophos are systematically investigated by performing the B3LYP/6-311++G(d,p), M06-2X/6-311++G(d,p) as well as MP2/6-311G(d) levels. Two possible mechanisms, the P–OR1 and P–OEt disintegration routes, are intensively studied; simultaneously, the concerted and stepwise neutral pathways are discussed at great length. In order to explore the effect of additional water, the hydrolysis channel in the presence of extra water is examined in detail. Moreover, the effect of solvent on water is evaluated by applying PCM model at M06-2X/6-311+G(d,p) method. Our results convincingly suggest that the stepwise processes are more favorable than the concerted ones and the most preferred mechanism seems to be the stepwise of P–OR1 rupture channel for the direct hydrolysis. The water-catalyzed hydrolysis is energetically preferred to the direct hydrolysis. Furthermore, the solvent effect has only a slight effect on the reaction mechanism.