摘要
采用以ＡＳＥＤＭＯ（含原子对排斥的ＥＨＭＯ法）为基础的结构自动优化的ＥＨＴＯＰＴ法，对共聚物铑配合物催化甲醇羰基化制乙酸反应速率控制步骤———氧化加成进行了理论研究。计算了不同共聚物配体形成的铑催化剂与碘甲烷的氧化加成反应途径，并得到反应活化能，分析了氧化加成反应过程中的电子转移和空间因素对活化能的影响，计算结果与实验结果是相符的，并从理论上解释了２乙烯基吡啶形成的共聚物铑配合物催化活性高于４乙烯基吡啶形成的共聚物铑配合物催化活性的原因。
A theoritical study on the reaction rate control step of the carbonylation of methanol to acetic acid catalyzed by copolymer coordinated rhodium has been investigated in terms of the ASED MO method(including atomic repellent energy).The energy barries of oxidative addition reactions for different systems were calculated.The electron transfer and space factor which influenced the activation energies during oxidative addition were studied.It showed that the calculating results were bassically in agreement with the experiment results.The differences of catalysis activity beween 2 vinylpridine system and 4 vinylpridine system were explained theoretically.
出处
《北京化工大学学报（自然科学版）》
CAS
CSCD
1998年第2期76-80,共5页
Journal of Beijing University of Chemical Technology(Natural Science Edition)
基金
国家自然科学基金
