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采用有效核势能近似(ECP)从头算方法,在HF/LANL2DZ水平下研究了羰基钴催化的氢甲酰化反应循环中的羰基插入、H2 氧化加成和脱氢还原系列基元反应步骤的反应机理.优化得到了反应基态势能面的中间体、过渡态和产物的几何构型.计算了反应活化位垒,并对各过渡态进行了振动分析以确认.理论计算结果表明,羰基插入、H2 氧化加成、脱氢还原的基元反应步骤的活化位垒分别为67.79、139.11和44.78kJ·mol-1.
Using the ab initio method of effective nuclear potential approximation (ECP), the reactions of carbonyl insertion, H2 oxidation addition and dehydrogenation reduction series of elementary reaction steps in the carbonyl cobalt catalyzed hydroformylation reaction were studied at the HF / LANL2DZ level Mechanism. The intermediates, transition states and product geometries of the potential energy surfaces of the ground state were optimized. The reaction activation barriers were calculated and the vibrational analyzes of the transition states were carried out to confirm. The theoretical calculations show that the carbonyl insertion, H2 Oxidative addition, dehydrogenation of the elementary reaction step barriers were 67.79,139.11 and 44.78kJ · mol-1.