Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada.
J Chem Theory Comput. 2005 May;1(3):353-62. doi: 10.1021/ct049918x.
The Staudinger reaction of phosphane and azide has been investigated by Atom-centered Density Matrix Propagation (ADMP) approach to ab initio molecular dynamics (AIMD) in combination with molecular orbital analysis within density functional theory. At room temperature, the reaction pathway with the cis initial attack dominates the Staudinger reaction. Electrostatic interaction, charge transfer, and covalent overlap are responsible for the initial attack and for the system to overcome the initial reaction barrier. The rotation of PH3 and PH vibrations facilitate the isomerization of the system from cis intermediate to the last transition state, which indicates that small substituent groups on phosphane can facilitate the last stage of the Staudinger reaction. During the course of the reaction, the change of the average polarizability correlates positively to the change of the potential energy of the system, which clearly suggests that polar solvents can facilitate the overall reaction by stabilizing all transition states and reducing all reaction barriers.
采用原子中心密度矩阵传播（ADMP）方法结合密度泛函理论中的分子轨道分析对膦和叠氮化物的施蒂丁格反应进行了从头分子动力学（AIMD）研究。在室温下，顺式初始进攻的反应途径占主导地位。静电相互作用、电荷转移和共价重叠是初始进攻的原因，也是系统克服初始反应势垒的原因。PH3 的旋转和 PH 振动促进了体系从中间体到最后过渡态的异构化，这表明膦上的小取代基可以促进施蒂丁格反应的最后阶段。在反应过程中，平均极化率的变化与体系势能的变化呈正相关，这清楚地表明极性溶剂可以通过稳定所有过渡态和降低所有反应势垒来促进整个反应。
