DFT研究Schrock钼催化剂催化的丙烯和丙烯腈复分解反应机理

使用密度泛函理论方法研究了Schrock钼催化剂催化的丙烯和丙烯腈复分解反应机理。研究结果表明：所有金属环丁烷中间体都是三角双锥结构，配体OCF₃和NMe占据三角双锥结构的2个顶点。大部分过渡态具有与金属环丁烷中间体相似的结构特征。Schrock钼催化剂催化的丙烯和丙烯腈的复分解反应包含了3个反应步骤。基于不同通道过渡态结构的相对能量，我们预测顺式和反式产物的产率为9∶1，这个结果与实验事实吻合得很好。

DFT Study on the Mechanism of Cross-Metathesis between Acrylonitrile and Propene Catalyzed by Schrock's Molybdenum Catalyst

Density functional theory calculations have been carried out to explore the mechanism of the cross-metathesis between acrylonitrile and propene molecules catalyzed by the Schrock's molybdenum catalyst. All intermediate metallacyclobutanes are in the trigonal bipyramidal geometry with axial OCF3 and NMe ligands. The transition states leading to the four-membered ring intermediate or decomposing this four-membered ring intermediate have most of the features of intermediate except the entering or leaving group even further away from metal alkylidene. Three independent steps are involved in the cross-metathesis. Based on the relative energies of the transition state structures leading to the cis and trans products, the equilibrium condensation ratio of the cis to trans products is predicted to be about 9:1, which is in good agreement with the experiment results.