镍催化芳烃卤化物还原性交叉偶联的反应机理
利用密度泛函理论（DFT）计算研究了镍催化的溴苯（R｜）与对溴苯甲酸甲酯（R2）生成非对称联芳化合物的还原性交叉偶联反应的机理．结果表明，相对于一价镍的催化机理，零价镍作为活性催化剂更有利于反应的进行，零价镍催化剂首先与R1络合或者首先与R2络合的反应机理十分相似，其决速步在气相时的能垒分别是70．50或者49．66kJ·mol^-1．零价镍催化机理包括如下步骤：一次氧化加成：还原：二次氧化加成：还原消除以及催化剂再生．另外，计算结果还表明有机锌试剂在这个反应体系中很难生成．...
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| Published in | 物理化学学报 Vol. 30; no. 5; pp. 821 - 828 |
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| Main Author | |
| Format | Journal Article |
| Language | Chinese |
| Published |
上海大学理学院化学系,上海,200444
2014
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| Subjects | |
| Online Access | Get full text |
| ISSN | 1000-6818 |
| DOI | 10.3866/PKU.WHXB201403241 |
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| Summary: | 利用密度泛函理论（DFT）计算研究了镍催化的溴苯（R｜）与对溴苯甲酸甲酯（R2）生成非对称联芳化合物的还原性交叉偶联反应的机理．结果表明，相对于一价镍的催化机理，零价镍作为活性催化剂更有利于反应的进行，零价镍催化剂首先与R1络合或者首先与R2络合的反应机理十分相似，其决速步在气相时的能垒分别是70．50或者49．66kJ·mol^-1．零价镍催化机理包括如下步骤：一次氧化加成：还原：二次氧化加成：还原消除以及催化剂再生．另外，计算结果还表明有机锌试剂在这个反应体系中很难生成． |
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| Bibliography: | 11-1892/06 Density functional theory; Nickel catalysis; Reductive cross-coupling;Reaction mechanism; Unsymmetrical biaryl The mechanism of the Ni-catalyzed reductive cross-coupling reaction of bromobenzene （R1） and methyl 4-bromobenzoate （R2） to form an unsymmetrical biaryl system has been theoretically investigated using density functional theory calculations. Our results showed that the Ni~-catalyzed process was favored over the Ni＇-catalyzed mechanism. The mechanism for the reaction of the Ni0 catalyst initially attacking either R1 or R2 was quite similar, where the energy barrier in the gas phase for the rate-limiting step was 70.50 or 49.66 kJ· mol-1, respectively. The mechanism in the favored Ni~-catalyzed reaction involved the following steps： first oxidative addition, reduction, second oxidative addition, reductive elimination, and catalyst regeneration. Our calculated results also indicated that no organometallic reagents were produced in the reaction cycle. JIANG Feng REN Qing-Hua （Department of Chemis |
| ISSN: | 1000-6818 |
| DOI: | 10.3866/PKU.WHXB201403241 |