Structural characterization and proton reduction electrocatalysis of thiolate-bridged bimetallic (CoCo and CoFe) complexes.
Using an assembly method, dinuclear CoCo and CoFe complexes supported by a bdt ligand, [Cp*Co(μ-η2:η2-bdt)(μ-I)CoCp*][PF6] (1[PF6], Cp* = η5-C5Me5, bdt = benzene-1,2-dithiolate), and [Cp*Co(μ-η2:η4-bdt)FeCp'][PF6] (3[PF6], Cp' = η5-C5Me4H) were synthesized in high yields. Upon chemical reduction with CoCp2, complexes 1[PF6] and 3[PF6] were converted to [Cp*Co(μ-η2:η2-bdt)CoCp*] (2) and [Cp*Co(μ-η2:η4-bdt)FeCp'][PF6] (3), respectively. Treatment of 2 with HBF4resulted in the protonation of two cobalt centers to generate a hydride bridged complex, [Cp*Co(μ-η2:η2-bdt)(μ-H)CoCp*][BF4] (4[BF4]), which was identified by spectroscopy and X-ray crystallography. When treating 3 with HBF4, a one-electron oxidation occurred to afford complex 3[BF4] along with the formation of H2. Importantly, heterodinuclear complex 3[PF6] and hydride bridged complex 4[BF4] can serve as effective catalysts to promote proton reduction for hydrogen evolution, as evidenced by cyclic voltammetry.
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Peng
P
Tong
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Wenjie
W
Xie
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Dawei
D
Yang
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Baomin
B
Wang
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Xiaoxiao
X
Ji
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Jianzhe
J
Li
State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Jingping
J
Qu