【摘要】 在 HF/LANL 2 DZ水平下 ,采用有效核势能近似 ( ECP)从头算方法 ,研究了有机膦配体改性羰基钴催化的氢甲酰化反应循环中部分基元反应步骤的微观反应机理 .优化了基态势能面上诸反应中间体、过渡态和产物的几何构型 .计算了反应活化位垒 .结果表明 ,羰基插入、加氢氧化和脱氢还原的基元反应步骤的活化位垒分别为 54.0 2 ,1 3 4 .0 2和 4 3 .4 4k J/mol更多还原

【Abstract】 All structural geometries of intermediates, transition states and product are optimized at HF/LANL2DZ level under the effective core potential approximation. The potential energy profile for some elementary reactions of hydroformylation catalyzed by Co 2(CO) 6(PH 3) 2, consisting of carbonyl insertion, H 2 oxidative addition and aldehyde reductive elimination, are calculated. The transition states are further confirmed by having one and only one imaginary vibrational frequency. The activation energies of carbonyl insertion, H 2 oxidative addition and aldehyde reductive elimination are 54.02, 134.02 and 43.44 kJ/mol, respectively.更多还原