Trinuclear Transition Metal Complexes in Catalytic Reactions

doi:10.6023/A22100425

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (1): 84-99.DOI: 10.6023/A22100425 Previous Articles Next Articles

Review

三核过渡金属配合物在催化反应中的研究进展

马雪璐^a^,^b^,^*(), 李蒙^a, 雷鸣^c^,^*()

a 中国矿业大学(北京) 化学与环境工程学院北京 100083
b 闽江学院福建省海洋传感功能材料重点实验室福州 350108
c 北京化工大学化工资源有效利用国家重点实验室计算化学研究所化学学院北京 100029

投稿日期:2022-10-11 发布日期:2022-12-05
通讯作者: 马雪璐, 雷鸣

作者简介:

马雪璐, 博士, 中国矿业大学(北京)化学与环境工程学院讲师, 硕士研究生导师. 2016年博士毕业于北京化工大学理学院(导师: 雷鸣教授); 同年进入清华大学化学系从事博士后研究工作(导师: 李隽教授). 2018年至今就职于中国矿业大学(北京)化学与环境工程学院, 主要研究方向为绿色催化反应体系的理论设计研究.

李蒙, 中国矿业大学(北京)2020级在读硕士研究生. 2015年获河北科技师范学院学士学位. 研究方向为均相催化剂的理论设计研究.

雷鸣, 北京化工大学化工资源有效利用国家重点实验室、计算化学研究所及化学学院物理化学系教授、博士生导师. 研究方向为计算催化化学. 在均相催化、多相催化催化机制、催化剂分子设计、理论计算化学及其交叉领域进行了探索性学术研究工作.

基金资助:
项目受中央高校基本科研业务费(2022YQHH01); 福建省海洋传感功能材料重点实验室(闽江学院)开放课题(MJUKF-FMSM202202); 国家自然科学基金(21902182)

Trinuclear Transition Metal Complexes in Catalytic Reactions

Xuelu Ma^a^,^b(), Meng Li^a, Ming Lei^c()

a School of Chemical & Environmental Engineering, China University of Mining & Technology, Beijing 100083
b Fujian Key Laboratory of Functional Marine Sensing Materials, Minjiang University, Fuzhou 350108
c State Key Laboratory of Chemical Resource Engineering, Institute of Computational Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029

Received:2022-10-11 Published:2022-12-05
Contact: ^*E-mail: maxl@cumtb.edu.cn; leim@mail.buct.edu.cn
Supported by:
Fundamental Research Funds for the Central Universities(2022YQHH01); Open Project Program of Fujian Key Laboratory of Functional Marine Sensing Materials(MJUKF-FMSM202202); National Natural Science Foundation of China(21902182)

Polynuclear transition metal complexes are widely used as homogeneous catalysts, and the polymetallic active sites of enzymes also play an important role in the mechanism of biochemical reactions under ambient conditions. As the efficient polymetallic catalysts for the activation of small molecules, trinuclear metal complexes have been attracted extensive attention. In order to understand the role of trinuclear transition metal complexes in catalytic reactions, we have classified the trinuclear transition metal complexes according to metal centers, and summarized the characteristics of their ligands, as well as their catalytic applications. Based on the metal centers, the geometric structure and electronic characteristics of the complexes are discussed. Based on the peripheral ligands, the characteristics of the coordination environment, which enable the aggregation of three independent metal sites, are highlighted. In terms of catalytic applications of trinuclear transition metal complexes, the catalytic mechanisms involving specific chemical bonds activation are focused on. Finally, we outlook the crucial potential application in this emerging ﬁeld.

Key words: trinuclear transition metal complexes, homogeneous catalysis, chemical bond activation, synergy mechanism

Cite this article

Xuelu Ma, Meng Li, Ming Lei. Trinuclear Transition Metal Complexes in Catalytic Reactions[J]. Acta Chimica Sinica, 2023, 81(1): 84-99.

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Fig. & Tab. 20

Figure 1. Homometallic trinuclear complexes of IIIB~VIIB group transition metals

Figure 2. Homometallic trinuclear complexes of VIII group transition metals

Figure 3. Homometallic trinuclear complexes of IB~IIB transition metals

Figure 4. Heterometallic trinuclear transition metal complexes

Figure 5. Closed cyclic ligands

Figure 6. Open cavity ligands

Figure 7. A series of trinuclear metal complexes based on the same ligand environment

Figure 8. Ligand characteristics of trinuclear metal complexes

Figure 9. Dinitrogen activation mechanism catalyzed by the trinuclear titanium complex 1[8]

Figure 10. Dinitrogen activation and hydrogenation by the trinuclear chromium tetrahydride complex 4[14]

Figure 11. The solid-state conversion of complex 51 to complex 51-A[78]

Figure 12. Dinitrogen activation catalyzed by the trinuclear cobalt complex 15[26,55]

Figure 13. Plausible mechanism for the reaction of trinuclear ruthenium complex 52 with substituted hydrazines[84]

Figure 14. Synthesis and the proposed formation mechanism of 37-C[49]

Figure 15. Proposed mechanism of the ring cleavage and contraction of benzene and toluene by the trinuclear titanium complex 1[89]

Figure 16. Activation of C=C/C≡C bond by the trinuclear palladium complex 53[91]

Figure 17. The plausible reaction mechanism for the catalytic hydrogenation of CO2 using the trinuclear iridium complex 54[92]

Figure 18. CO2 fixation in the presence of tripodal Zn complex 33[45]

Figure 19. Hydrodenitrification and transformation of pyridine catalyzed by the trinuclear titanium complex 1 [10]

Figure 20. The plausible reaction mechanism of the oxidation of methane to methanol mediated by trinuclear copper complex 30[38]

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	( 马雪璐, 大学化学, 2020, 35, 47.)

三核过渡金属配合物在催化反应中的研究进展

Trinuclear Transition Metal Complexes in Catalytic Reactions

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