Tetranuclear Iron Complexes Bearing Benzenetetrathiolate Bridges as Four-Electron Transformation Templates and Their Electrocatalytic Properties for Proton Reduction - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2013

Tetranuclear Iron Complexes Bearing Benzenetetrathiolate Bridges as Four-Electron Transformation Templates and Their Electrocatalytic Properties for Proton Reduction

Résumé

Two tetranuclear iron–sulfur complexes, (μ,μ-pbtt)[Fe2(CO)6]2 (pbtt = benzene-1,2,4,5-tetrathiolato, 3) and (μ,μ-obtt)[Fe2(CO)6]2 (obtt = benzene-1,2,3,4-tetrathiolato, 4), were prepared from reaction of Fe3(CO)12 and the corresponding tetramercaptobenzene in THF, respectively. Complexes 5 and 6, (μ,μ-pbtt)[Fe2(CO)5L1][Fe2(CO)5L2] (L1 = CO, L2 = PPyr3 (Pyr = N-pyrrolyl), 5; L1 = L2 = PPyr3, 6) were obtained by controlling CO displacement of 3 with PPyr3. Molecular structures of 3–6 were determined by spectroscopic and single-crystal X-ray analyses. All-CO Fe4S4 complexes 3 and 4 each display four-electron reduction processes in consecutive chemically reversible two-electron reduction events with relatively narrow potential spans in the cyclic voltammograms. Phosphine-substituted Fe4S4 complexes 5 and 6 exhibit two consecutive two-electron reduction events, which are not fully reversible. The electrocatalytic properties of 3 and 4 for proton reduction were studied using a series of carboxylic acids of increasing strength (CH3COOH, CH2ClCOOH, CHCl2COOH, CCl3COOH, and CF3COOH). The mechanisms for electrochemical proton reduction to hydrogen catalyzed by complex 3 as a function of acid strength are discussed

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hal-02283956 , version 1 (11-09-2019)

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Lin Chen, Mei Wang, Frederic Gloaguen, Dehua Zheng, Peili Zhang, et al.. Tetranuclear Iron Complexes Bearing Benzenetetrathiolate Bridges as Four-Electron Transformation Templates and Their Electrocatalytic Properties for Proton Reduction. Inorganic Chemistry, 2013, 52 (4), pp.1798--1806. ⟨10.1021/ic301647u⟩. ⟨hal-02283956⟩
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