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Article Dans Une Revue Inorganics Année : 2019

Electronic Communication between Dithiolato-Bridged Diiron Carbonyl and S-Bridged Redox-Active Centres

Résumé

The catalytic potential of linked redox centres is exemplified by the catalytic site of [FeFe]-hydrogenases, which feature a diiron subsite linked by a cysteinyl S atom to a 4Fe4S cube. The investigation of systems possessing similarly-linked redox sites is important because it provides a context for understanding the biological system and the rational design of abiological catalysts. The structural, electrochemical and spectroscopic properties of Fe 2 (CO) 5 (CH 3 C(CH 2 S) 2 CH 2 SPhNO 2 , I-bzNO 2 and the aniline analogue, I-bzNH 2 , are described and IR spectroelectrochemical studies have allowed investigation of the reduction products and their reactions with CO and protons. These measurements have allowed identification of the nitrobenzenyl radical anion, quantification of the shifts of the (CO) bands on ligand-based reduction compared with NO 2 /NH 2 exchange and protonation of the pendent ligand. The strength of thioether coordination is related to the electronic effects, where competitive binding studies with CO show that CO/thioether exchange can be initiated by redox processes of the pendent ligand. Stoichiometric multi electron/proton transfer reactions of I-bzNO 2 localised on nitrobenzene reductions occur at mild potentials and a metal-centred reduction in the presence of protons does not lead to significant electrocatalytic proton reduction.
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Dates et versions

hal-02067244 , version 1 (14-03-2019)

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Cédric Tard, Stacey Borg, Shirley Fairhurst, Christopher Pickett, Stephen Best. Electronic Communication between Dithiolato-Bridged Diiron Carbonyl and S-Bridged Redox-Active Centres. Inorganics, 2019, 7 (3), pp.37. ⟨10.3390/inorganics7030037⟩. ⟨hal-02067244⟩
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