Ab initio study on the mechanism of rhodium-complex-catalyzed carbonylation of methanol to acetic acid  

作　　者：雷鸣 冯文林 郝茂荣 冀永强 徐振锋 

出　　处：《Science China Chemistry》2001年第5期465-472,共8页中国科学（化学英文版）

基　　金：the Young Teachers' Foundation of Beijing University of Chemical Technology (Grant No. QN0018).

摘　　要：The whole catalytic cycle of the carbonylation of methanol to acetic acid catalyzed by Rh complex is theoretically studied. All structural geometries of reactant, intermediates, transition states and product are optimized at HF/LANL2DZ level under the ECP approximation. The potential energy profiles for elementary reactions of carbonylation are calculated respectively. The transition states are further confirmed by having one and only one imaginary vibrational frequency. The results indicate that the activation energy values of CHin3I oxidative addition, carbonyl insertion and CH3COI reductive elimination fundamental steps are 216.03, 128.10 and 126.55 kJ/mol, respectively; and that the CH3I oxidative addition step is predicted to be the rate-determining one.The whole catalytic cycle of the carbonylation of methanol to acetic acid catalyzed by Rh complex is theoretically studied. All structural geometries of reactant, intermediates, transition states and product are optimized at HF/LANL2DZ level under the ECP approximation. The potential energy profiles for elementary reactions of carbonylation are calculated respectively. The transition states are further confirmed by having one and only one imaginary vibrational frequency. The results indicate that the activation energy values of CH3I oxidative addition, carbonyl insertion and CH3COI reductive elimination fundamental steps are 216.03, 128.10 and 126.55 kJ/mol, respectively; and that the CH3I oxidative addition step is predicted to be the rate-determining one.

关 键 词：rhodium complex CARBONYLATION ab initio method effective core potential 

分 类 号：O643.3[理学—物理化学]