Citation: Chao Guo, Linan Su, Dawei Yang, Baomin Wang, Jingping Qu. Synthesis, characterization and reactivity of thiolate-bridged cobalt-iron and ruthenium-iron complexes[J]. Chinese Chemical Letters, ;2022, 33(1): 217-220. doi: 10.1016/j.cclet.2021.06.070 shu

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

Chao Guo ^a ,
Linan Su ^{a, *,} ,
Dawei Yang ^a ,
Baomin Wang ^a ,
Jingping Qu ^{a, b}

a.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
b.
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

lnsu@dlut.edu.cn

Received Date: 22 April 2021
Revised Date: 22 June 2021
Accepted Date: 25 June 2021
Available Online: 3 July 2021

Figures(5)

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 Co^IIFe^II 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.
- Metallic cooperativity,
- Heterobinuclear complex,
- Hydrazine disproportionation,
- Metallothiolate ligand,
- Metal-sulfur cluster
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