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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Structural characterization and proton reduction electrocatalysis of thiolate-bridged bimetallic (CoCo and CoFe)
Peng Tong1, Wenjie Xie1, Dawei Yang1
1State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian, 116024, P.R. China. qujp@dlut.edu.cn.
Abstract:
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 HBF4 resulted 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.
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