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用量子化学的方法计算了3,5-二硝基苯甲酸离子和一系列吲哚取代的羧酸衍生物的休克尔分子轨道及相关参数。研究了这类羧酸衍生物形成传荷络合物前后的π-电荷密度的变化值。计算结果指出:传荷络合物的稳定性及其对水解反应的致钝效应与电荷转移的区域和程度成正比。同时由于共轭体系的存在,给予体的电荷转移部位不仅局限于吲哚环,因此由传荷络合作用所造成的空间位阻和静电排斥对阻滞水解反应也有一定的影响。
Quantum chemistry method was used to calculate the Hückel molecular orbitals and related parameters of 3,5-dinitrobenzoate ion and a series of indole-substituted carboxylic acid derivatives. The change of π-charge density before and after the formation of charge-transfer complexes with these carboxylic acid derivatives was studied. The calculated results show that the stability of the charge-transfer complex and its blunted effect on the hydrolysis reaction are proportional to the region and degree of charge transfer. At the same time, due to the existence of conjugated system, the charge transfer sites of donors are not limited to indole rings. Therefore, the steric hindrance and electrostatic repulsion caused by the charge-transfer complexation also have certain influence on the block hydrolysis reaction.