论文部分内容阅读
本文用EHMO法计算了饱和烃以端基及侧基配位到催化剂活性种PtCl_3(H_2O)~-的d_(z~2)/d_(x~2-y~2)混合轨道上体系的总能量.结果表明,以端基的方式进行配位较之侧基有利.还计算了反应速率控制步骤中生成过渡态的势垒和主要原子的净电荷的变化,从而阐明了控制步骤的机理是双核配合物分子内靠近氢根配体的桥联氯离子转移到烷基上的还原消去反应.理论计算与实验结果一致.
The EHMO method was used to calculate the ratio of the total amount of saturated hydrocarbons to the d_ (z ~ 2) / d_ (x ~ 2-y ~ 2) mixed orbitals of the active species PtCl_3 (H_2O) ~ Energy.The results show that the coordination of terminal groups is more beneficial than that of the side groups.The change of the net charge of the transition barrier and the primary atoms in the reaction rate control step is also calculated and the mechanism of the control step The reductive elimination reaction of the bridged chloride ion near the hydrogen-based ligand in the dinuclear complex molecule to the alkyl group is theoretically calculated and the experimental results are consistent.