| 改性羰基钴催化氢甲酰化反应系列基元反应的理论研究 |
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| 引用本文： | 雷鸣,冯文林,徐振锋,徐恒连. 改性羰基钴催化氢甲酰化反应系列基元反应的理论研究[J]. 高等学校化学学报, 2001, 22(3): 455-459 |
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| 作者姓名： | 雷鸣 冯文林 徐振锋 徐恒连 |
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| 作者单位： | 1. 北京化工大学应用化学系, 北京 100029;2. 北京师范大学化学系, 北京 100875;3. 中国科学院长春应用化学研究所, 长春 130022 |
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| 摘 要： | 在HF/LANL2DZ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54.02,134.02和43.44kJ/mol.
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| 关 键 词： | 改性羰基钴 有机膦配体 氢甲酰化反应 从头算 赝势法 |
| 文章编号： | 0251-0790(2001)03-0455-05 |
| 收稿时间： | 1999-11-30 |
Theoretical Study on the Mechanisms of Some Elementary Reactions Catalyzed by Modified Carbonyl Cobalt |
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| LEI Ming,FENG Wen-Lin,XU Zhen-feng,XU HengLian. Theoretical Study on the Mechanisms of Some Elementary Reactions Catalyzed by Modified Carbonyl Cobalt[J]. Chemical Research In Chinese Universities, 2001, 22(3): 455-459 |
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| Authors: | LEI Ming FENG Wen-Lin XU Zhen-feng XU HengLian |
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| Affiliation: | 1. Department of Applied Chemistry, Beijing University of Chemical Technology, Beijing 100029, China;2. Department of Chemistry, Beijing Normal University, Beijing 100875, China;3. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China |
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| 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. |
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| Keywords: | Modified carbonyl cobalt Organic phosphorus ligand Hydroformylation Ab initio method Effective core potential |
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