Synthesis,characterization and reactivity of thiolate-bridged cobalt-iron and ruthenium-iron complexes  

作　　者：Chao Guo Linan Su Dawei Yang Baomin Wang Jingping Qu 

机构地区：[1]State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,China [2]State Key Laboratory of Bioreactor Engineering,Shanghai Collaborative Innovation Centre for Biomanufacturing,Frontiers Science Center for Materiobiology and Dynamic Chemistry,East China University of Science and Technology,Shanghai 200237,China

出　　处：《Chinese Chemical Letters》2022年第1期217-220,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21690064,22001031);the key laboratory of Bio-based Chemicals of Liaoning Province of China;the“111”project of the Ministry of Education of China;the Fundamental Research Funds for the Central Universities(No.DUT19RC(3)013)。

摘　　要：Thiolate-bridged hetero-bimetallic complexes[Cp^(*)M(MeCN)N_(2)S_(2)FeCl][PF_(6)](2,M=Ru;3,M=Co,Cp^(*)=η^(5)-C_(5)Me_(5),N_(2)S_(2)=N,N'-dimethyl-3,6-diazanonane-1,8-dithiolate)were prepared by self-assembly of dimer[N_(2)S_(2)Fe]2 with mononuclear precursor[Cp^(*)Ru(MeCN)_(3)][PF_(6)]or[Cp^(*)Co(MeCN)_(3)][PF_(6)]_(2)in the presence of CHCl_(3)as a chloride donor.Complexes 2 and 3 exhibit obviously different redox behaviors investigated by cyclic voltammetry and spin density distributions supported by DFT calculations.Notably,iron-cobalt complex 3 possesses versatile reactivities that cannot be achieved for complex 2.In the presence of CoCp_(2),complex 3 can undergo one-electron reduction to generate a stable formally Co^(II)Fe^(II)complex[Cp^(*)CoN_(2)S_(2)FeCl](4).Besides,the terminal chloride on the iron center in 3 can be removed by dehalogenation agent AgPF_(6)or exchanged with azide to afford the corresponding complexes[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(MeCN)][PF_(6)]_(2)(5)and[Cp^(*)Co(MeCN)N_(2)S_(2)Fe(N_(3))][PF_(6)](6).In addition,complexes 2,3 and 4 show distinct catalytic reactivity toward the disproportionation of hydrazine into ammonia.These results may be helpful to understand the vital role of the heterometal in some catalytic transformations promoted by heteromultinuclear complexes.

关 键 词：Metallic cooperativity Heterobinuclear complex Hydrazine disproportionation Metallothiolate ligand Metal-sulfur cluster 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]