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

doi:10.7503/cjcu20170652

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (4): 721.doi: 10.7503/cjcu20170652

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

张尉¹, 张益伟¹, 李慧^1,², 雷鸣¹()

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

收稿日期:2017-09-29 出版日期:2018-04-10 发布日期:2018-03-21
作者简介:联系人简介: 雷鸣, 男, 博士, 教授, 博士生导师, 主要从事计算催化化学方面的研究. E-mail:leim@mail.buct.edu.cn
基金资助:
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)和中央高校科研业务费(批准号: PYCC1708)资助

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

ZHANG Wei¹, ZHANG Yiwei¹, LI Hui^1,², LEI Ming^1,^*()

1. State Key Laboratory of Chemical Resource Engineering, College of Science,Beijing University of Chemical Technology, Beijing 100029, China
2. Chemical Science and Engineering College, North Minzu University, Yinchuan 750021, China

Received:2017-09-29 Online:2018-04-10 Published:2018-03-21
Contact: LEI Ming E-mail:leim@mail.buct.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21672018, 21373023), the Natural Science Foundation of Beijing City, China(No.2162029) and the Fundamental Research Funds for the Central Universities, China(No.PYCC1708)

摘要/Abstract

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(^iPrPNP)CoOR的反应机理进行了理论研究. 结果表明, 在反应过程中(^iPrPNP)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(^iPrPNP)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(^iPrPNP)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.

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

Abstract:

The reaction mechanism of Co(Ⅰ) complex (^iPrPNP)CoOR 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.

Key words: Transition metal cobalt complex, Dissociative path, Density functional theory, Concerted mechanism

中图分类号:

O643.31

TrendMD:

张尉, 张益伟, 李慧, 雷鸣. 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. 高等学校化学学报, 2018, 39(4): 721.

ZHANG Wei, ZHANG Yiwei, LI Hui, LEI Ming. Theoretical Study on the Formation Mechanism of Catalytic Active Components in Suzuki-Miyaura Cross-Coupling Reaction Catalyzed by Transition Metal Cobalt Complex^†. Chem. J. Chinese Universities, 2018, 39(4): 721.

图/表 10

Sceheme 1 Oxidation addition step in Ni-catalyzed Suzuki-Miyaura cross-coupling reaction of aryl O-carbamates and O-sulfamates[10]

Scheme 2 Plausible catalytic cycle for cobalt-catalyst promote Suzuki-Miyaura coupling reaction[9]

Scheme 3 Preparation of (iPrPNP)CoOR complexes with (iPrPNP)CoCH2SiMe3 and HOR(R=CH3)[9]

Fig.1 Ligand(iPrPNP) dissociative path and non-dissociative path for the formation of (iPrPNP)CoOCH3(INT4)

Fig.2 Structural parameters of (iPrPNP)CoCH3 complex at triplet(A) and singlet(B)For clarity H atoms of the (iPrPNP)CoCH3 complex are not shown. The values inside and outside the brackets represent the calculated data and experimental data, respectively. The symbol na indicates that the experimental data is unknown. Bond lengths are in nm, bond angles are in degree.

Fig.3 Energy profiles for the concerted mechanism of (iPrPNP)CoOCH3(INT4) formation via the dissociative and non-dissociative path

Fig.4 Energy profiles for the stepwise mechanism of (iPrPNP)CoOCH3(INT4) formation via the dissociative path

Fig.5 Energy profiles for the stepwise mechanism of (iPrPNP)CoOCH3(INT4) formation via the non-dissociative path

Fig.6 Key structural parameters of INT2', INT3', TS1 and TS3 complexs at triplet stateFor clarity, H atoms of the iPrPNP ligands and CH2SiMe3 are not shown. Bond lengths are in nm.

Fig.7 Energy profiles for the (iPrPNP)CoOR(INT4) formation(R= Me, Et, iPr,and CH(Me)Ph) via the dissociative path

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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^†

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