物理化学学报Issue(5)：821-828,8.DOI:10.3866/PKU.WHXB201403241
镍催化芳烃卤化物还原性交叉偶联的反应机理
Reaction Mechanism for the Ni-Catalyzed Reductive Cross-Coupling of Aryl Halides
摘要
Abstract
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 theoretical y investigated using density functional theory calculations. Our results showed that the Ni0-catalyzed process was favored over the NiI-catalyzed mechanism. The mechanism for the reaction of the Ni0 catalyst initial y 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 Ni0-catalyzed reaction involved the fol owing 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.关键词
密度泛函理论/镍催化/还原性交叉偶联/反应机理/不对称联苯Key words
Density functional theory/Nickel catalysis/Reductive cross-coupling/Reaction mechanism/Unsymmetrical biaryl分类
化学化工引用本文复制引用
蒋峰,任清华..镍催化芳烃卤化物还原性交叉偶联的反应机理[J].物理化学学报,2014,(5):821-828,8.基金项目
The project was supported by the High Performance Computing Platform of Shanghai University, China and Shanghai Higher Education Connotation Construction“085”Project“Materials Genome Engineering”Funding, China (B.58-B111-12-101, B.58-B111-12-103).上海大学高性能计算平台“自强4000”与上海市高等教育内涵建设“085”工程“材料基因工程”项目(B.58-B111-12-101, B.58-B111-12-103)资助 （B.58-B111-12-101, B.58-B111-12-103）
