Synthesis,characterization and reactivity of thiolate-bridged cobalt-iron and ruthenium-iron complexes |
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| Authors: | Chao Guo Linan Su Dawei Yang Baomin Wang Jingping Qu |
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| Institution: | 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 |
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| Abstract: | 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 presence 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. Notably, 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 removed 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. |
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