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Synthesis and electrochemical investigations of the ortho-metalated complexes [Fe2(CO)6{к,μ-S,η2-(R)}] and their substitution reactions

[Display omitted] •[FeFe]-hydrogenase mimics produce electrochemically hydrogen from acetic acid.•Monosubstitution of ortho-metalated diiron hexacarbonyl complexes with PPh3.•Reactions of aromatic thioketones followed by 1,3-H shift lead to the ortho-metalated diiron hexacarbonyl complexes. Modifica...

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Published in:Inorganica Chimica Acta 2020-04, Vol.503, p.119377, Article 119377
Main Authors: Daraosheh, Ahmad Q., Abul-Futouh, Hassan, Görls, Helmar, Weigand, Wolfgang
Format: Article
Language:English
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Summary:[Display omitted] •[FeFe]-hydrogenase mimics produce electrochemically hydrogen from acetic acid.•Monosubstitution of ortho-metalated diiron hexacarbonyl complexes with PPh3.•Reactions of aromatic thioketones followed by 1,3-H shift lead to the ortho-metalated diiron hexacarbonyl complexes. Modifications of the dithiolate linkers that connect the two iron atoms of the synthetic H-cluster mimics of [FeFe]-hydrogenase play a significant role on tuning its physical and electrochemical properties. In this report, we describe the redox properties and the catalytic behavior of the ortho-metalated complexes having the general formula [Fe2(CO)6{к,μ-S,η2-(R)}] (R = C13H8OS, 1 and C17H20N2S, 2) in the presence and absence of acetic acid, AcOH as a proton source. Moreover, we explore the influence of substituting one CO in complex 1 by stronger electron donating, PPh3 toward the electrochemical reduction mechanism of the resulting substituted model complex [Fe2(CO)5PPh3{к,μ-S,η2-(C13H8OS)}], 3. Overall, the reduction of complexes 1–3 proceeds via simple EE mechanism (E = electron transfer) in the absence of AcOH. In Addition, all complexes show their ability to catalyze the reduction of protons and generate H2 in the presence of AcOH.
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2019.119377