过渡金属钴配合物催化Suzuki-Miyaura交叉偶联反应催化活性组分生成机理的理论研究  

Theoretical Study on the Formation Mechanism of Catalytic Active Components in Suzuki-Miyaura Cross-Coupling Reaction Catalyzed by Transition Metal Cobalt Complex

作　　者：张尉 张益伟[1] 李慧 雷鸣[1] ZHANG Wei;ZHANG Yiwei;LI Hui;LEI Ming(State Key Laboratory of Chemical Resource Engineering, College of Science, Belling University of Chemical Technology, Beijing 100029, China;Chemical Science and Engineering College, North Minzu University, Yinchnan 750021, China)

机构地区：[1]北京化工大学理学院,化工资源有效利用国家重点实验室,北京100029 [2]北方民族大学化学与化学工程学院,银川750021

出　　处：《高等学校化学学报》2018年第4期721-728,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号：21672018,21373023); 北京市自然科学基金(批准号：2162029); 中央高校科研业务费(批准号：PYCC1708)资助

摘　　要：采用密度泛函理论(DFT)对过渡金属钴配合物催化Suzuki-Miyaura交叉偶联反应生成Co(Ⅰ)配合物(^(iPr)PNP)Co OR的反应机理进行了理论研究.结果表明,在反应过程中(^(iPr)PNP)配体中的一个膦配体从金属中心解离生成INT1',且三重态下的解离路径为优势反应路径;由INT1'生成Co(I)配合物(^(iPr)PNP)CoOR的解离反应路径中协同机理比分步机理更具优势;对底物ROH[R=Me,Et,~iPr,CH(Ph)Me]的R基团进行了调变,研究了生成(^(iPr)PNP)CoOR的解离路径的协同机理和分步机理中底物基团调变效应,当R=~iPr时反应的能垒最高.The reaction mechanism of Co（ Ⅰ） complex（^iPrPNP） Co OR formation in Suzuki-Miyaura cross-coupling reaction catalyzed by cobalt complex was studied via density functional theory（ DFT） calculation. The calculated results indicate that a phosphine ligand in the diisopropyl-substituted bis（ phosphino） pyridine pincer ligand（^iPrPNP） is dissociated from the Co metal center to produce INT1＇,the dissociative path at triplet state is the most favorable reaction path to form（^iPrPNP） CoOR than the non-dissociative path. The concerted mechanism of Co（ Ⅰ） complex（^iPrPNP） CoOR produced by INT1＇ is more favorable than the stepwise mechanism in the dissociative path. The effect of substituent groups of substrate HOR was studied,which in agreement with experimental observations. The reaction mechanism could provide a theoretical insight into the whole Suzuki-Miyaura cross-coupling reaction mechanism.

关 键 词：过渡金属钴配合物 配体解离 密度泛函理论 协同机理 

分 类 号：O643.31[理学—物理化学]