氯化钕异丙醇配合物的电子结构与络合活化的研究

本文用INDO方法计算了氯化钕异丙醇配合物的电子结构。计算结果指出, 配位后, 与Nd-Cl键对应的分子轨道能量升高, Nd-Cl键级降低, Nd的正电荷降低, Cl的负电荷增多。从而表明。由于配位发生轨道重迭, 使得异丙醇氧的孤对电子移向钕离子的空价轨道。钕离子上的电子云密度增高加强了对Nd—Cl键的价电子的推斥作用, 使Nd-Cl间的价电子密度减小, 导致Nd-Cl键的削弱, 降低了键的能量, 有效地活化了Nd-Cl键,有利于生成活性物种的烷基化反应的进行。同时表明, 对Nd-Cl的络合催化有某种选择性。

STUDY ON ELECTRONIC STRUCTURE AND COMPLEX ACTIVATION OF NEODYMIUM CHLORIDE COMPLEX WITH ISOPROPANOL

The molecular orbital energy, charge distribution, and Mulliken's bond order in neodymium chloride complex with isopropanol have been calculated with an INDO method. The calculation showed that after coordination, the molecular orbi tal energies corresponding to Nd—Cl bond were increased, the Nd—Cl bond orders were decreased, and the net charges on Nd and Cl were decreased. The results indi cate that the charge transfer of Cl→Nd caused by orbital overlapping and the re pulsion of negative charge added on Nd against the valent charge of Nd—Cl lead to increasing the energy levels and weakening the Nd—Cl bonds, which effectively activates the Nd—Cl bonds. It can be expected that the alkylation reaction to form active species may be favorably carried out.Besides, the complex activation for Nd—Cl is of certain choice.