Dinitrogen Functionalization Affording Structurally Well-Defined Cobalt Diazenido Complexes  

作　　者：Mingdong Zhong Xianlu Cui Botao Wu Gao-Xiang Wang Wen-Xiong Zhang Junnian Wei Lili Zhao Zhenfeng Xi 

机构地区：[1]Beijing National Laboratory for Molecular Sciences(BNLMS),Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,College of Chemistry,Peking University,Beijing 100871 [2]Institute of Advanced Synthesis,School of Chemistry and Molecular Engineering,Jiangsu National Synergetic Innovation Center for Advanced Materials,Nanjing Tech University,Nanjing 211816

出　　处：《CCS Chemistry》2022年第2期532-539,共8页中国化学会会刊（英文）

基　　金：supported by the Basic Science Center of Transformation Chemistry of Key Components of Air,National Natural Science Foundation of China(no.21988101);M.Z.acknowledges China Postdoctoral Science Foundation(no.2019M650294);L.Z.acknowledges the financial support from NSFC(nos.21973044 and 21703099);Natural Science Foundation of Jiangsu Province for Youth(no.BK20170964)。

摘　　要：Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.

关 键 词：bidentate phosphine ligand cobalt-bis(dinitrogen)complex cobalt diazenido complex dinitrogen functionalization dinitrogen silylation EDA-NOCV method 

分 类 号：O64[理学—物理化学]