共聚物铑配合物催化甲醇羰基化速控步骤的理论研究

THEORETIRAL STUDY OF THE REACTION RATE CONTROL STEP ON THE CARBONYLATION OF METHANOL TO ACETIC ACID CATALYZED BY COPOLYMERCOORDINATED RHODIUM

采用以原子重叠及电子离域的分子轨道理论ＡＳＥＤＭＯ（含原子对排斥的ＥＨＭＯ法）为基础的结构自动优化法，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 of the reaction rate control step on the carbonlation of methanol to acetic acid catalyzed by copolymercoordinated rhodium has been investigated in terms of the ASED MO method(including atomic repellent energy).The energy barriers of oxidative addition reactions for different systems were calculated.The way of electron transfer and space factor influencing the activation energies during oxidative addition were studied.It showed that the calculating results were bassically in agreement with the experimental results.The differences of catalysis activity between 2 vinylpridine system and 4 vinylpridine system were explained theoretically.