过氧化氢与苯乙烯环氧化的反应机理及溶剂效应

以过氧化氢与苯乙烯环氧化为模型反应, 采用Materials Studio软件中Dmol³模块, 模拟计算了过氧化氢与苯乙烯的环氧化反应机理. 并用连续介质-类导体屏蔽模型(COSMO)研究了反应体系分别在三种质子性溶剂(水, 乙醇, 叔丁醇)中的溶剂化效应. 为研究溶剂分子直接参与反应的微观过程, 用离散介质模型模拟了单个水分子、乙醇分子和叔丁醇分子分别对反应的影响. 两种溶剂模型所得的结果一致, 叔丁醇作溶剂时反应活性最好, 乙醇次之; 质子性溶剂能够促进过氧化氢分子的异裂, 形成活性氧物种, 从而使反应能垒降低.

Reaction Mechanism and Solvent Effects of Styrene Epoxidation with Hydrogen Peroxide

In this paper,styrene epoxidation with hydrogen peroxide was used as a model reaction.The Dmol3 implementation in the Materials Studio Software was used to simulate the mechanism of the model reaction.Solvent effects in the reaction were also studied using the conductor-like screening model(COSMO) as a part of the continuum model in three solvents:water,ethanol,and tert-butyl alcohol.To investigate the micro-process wherein the solvent molecules react with the solute molecules directly,the discrete model wa...