title: Synthesis and Electrocatalytic Property of Diiron Hydride Complexes Derived from a Thiolate-Bridged Diiron Complex.
abstract: Interaction of a diiron thiolate-bridged complex, [Cp*Fe(μ-η(2):η(4)-bdt)FeCp*] (1) (Cp* = η(5)-C5Me5; bdt = benzene-1,2-dithiolate) with a proton gives an Fe(III)Fe(III) hydride bridged complex, [Cp*Fe(μ-bdt)(μ-H)FeCp*][BF4] (3[BF4]). According to in situ variable temperature (1)H NMR studies, the formation of 3[BF4] was evidenced to occur through a stepwise pathway: protonation occurring at an iron center to produce terminal hydride [Cp*Fe(μ-bdt)(t-H)FeCp*][BF4] (2) and subsequent intramolecular isomerization to bridging hydride 3[BF4]. A one-electron reduction of 3[BF4] by CoCp2 affords a paramagnetic mixed-valent Fe(II)Fe(III) hydride complex, [Cp*Fe(μ-η(2):η(2)-bdt)(μ-H)FeCp*] (4). Further, studies on protonation processes of diruthenium and iron-ruthenium analogues of 1, [Cp*M1(μ-bdt)M2Cp*] (M1 = M2 = Ru, 5; M1 = Fe, M2 = Ru, 8), provide experimental evidence for terminal hydride species at these bdt systems. Importantly, diiron or diruthenium hydride bridged complexes 3[BF4], 7[BF4] and iron-ruthenium heterodinuclear complex 8[PF6] can realize electrocatalytic hydrogen evolution.
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Dawei
authors.initials: D
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Yang
authors.initials: Y
authors.lastname: Li
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Baomin
authors.initials: B
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Xiangyu
authors.initials: X
authors.lastname: Zhao
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Linan
authors.initials: L
authors.lastname: Su
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Si
authors.initials: S
authors.lastname: Chen
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Peng
authors.initials: P
authors.lastname: Tong
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Yi
authors.initials: Y
authors.lastname: Luo
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology , 2 Linggong Road, Dalian 116024, P. R. China.
authors.forename: Jingping
authors.initials: J
authors.lastname: Qu
mesh_terms: D002384:Catalysis; D004563:Electrochemistry; D058085:Iron Compounds / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D058085:Iron Compounds; D013438:Sulfhydryl Compounds