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论文类型：期刊论文

发表时间：2016-11-22

发表刊物：DALTON TRANSACTIONS

收录刊物：SCIE、EI、PubMed

卷号：45

期号：46

页面范围：18559-18565

ISSN号：1477-9226

摘要：Using an assembly method, dinuclear CoCo and CoFe complexes supported by a bdt ligand, [Cp*Co (mu-eta(2):eta(2)-bdt)(mu-I) CoCp*][PF6] (1[PF6], Cp* =. eta(5)-C5Me5, bdt = benzene-1,2-dithiolate), and [Cp*Co (mu-eta(2):eta(4)-bdt)FeCp'][PF6] (3[PF6], Cp' =. eta(5)-C5Me4H) were synthesized in high yields. Upon chemical reduction with CoCp2, complexes 1[PF6] and 3[PF6] were converted to [Cp*Co(mu-eta(2):eta(2)-bdt)CoCp*] (2) and [Cp*Co(mu-eta(2):eta(4)-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(mu-eta(2):eta(2)- bdt)(mu-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 H-2. 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.