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

• 作 者: Chao Guo Linan Su Dawei Yang Baomin Wang Jingping Qu
• 机 构: State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,China;State Key
• 出 处: 中国化学快报（英文版）
• 发表日期: 2022年1期
• 关键词: Metallic cooperativity Heterobinuclear complex Hydrazine disproportionation Meta

Thiolate-bridged hetero-bimetallic complexes[Cp*M(MeCN)N2S2FeCl][PF6](2,M =Ru;3,M =Co,Cp*=η5-C5Me5,N2S2 =N,N\'-dimethyl-3,6-diazanonane-1,8-dithiolate) were prepared by self-assembly of dimer[N2S2Fe]2 with mononuclear precursor[Cp*Ru(MeCN)3][PF6]or[Cp*Co(MeCN)3][PF6]2 in the pres-ence of CHCl3 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.No-tably,iron-cobalt complex 3 possesses versatile reactivities that cannot be achieved for complex 2.In the presence of CoCp2,complex 3 can undergo one-electron reduction to generate a stable formally CoⅡFeⅡ complex[Cp*CoN2S2FeCl](4).Besides,the terminal chloride on the iron center in 3 can be re-moved by dehalogenation agent AgPF6 or exchanged with azide to afford the corresponding complexes[Cp*Co(MeCN)N2S2Fe(MeCN)][PF6]2 (5) and[Cp*Co(MeCN)N2S2Fe(N3)][PF6](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.