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Open AccessArticle

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

1
LCM, CNRS, Ecole Polytechnique, Institut Polytechnique de Paris, 91128 Palaiseau, France
2
School of Chemistry, The University of Melbourne, Parkville 3010, Australia
3
John Innes Centre, Norwich Research Park, Norwich NR4 7UH, UK
4
School of Chemistry, University of East Anglia, Norwich NR4 7TJ, UK
*
Authors to whom correspondence should be addressed.
Inorganics 2019, 7(3), 37; https://doi.org/10.3390/inorganics7030037
Received: 31 January 2019 / Revised: 1 March 2019 / Accepted: 2 March 2019 / Published: 8 March 2019
(This article belongs to the Special Issue Binuclear Complexes)
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 Fe2(CO)5(CH3C(CH2S)2CH2SPhNO2, I-bzNO2 and the aniline analogue, I-bzNH2, 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 NO2/NH2 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-bzNO2 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. View Full-Text
Keywords: [FeFe]-hydrogenase model compounds; electrochemistry; spectroelectrochemistry; infrared spectroscopy; dithiolato-bridged diiron carbonyl compounds; ligand substitution reactions; coupled electron proton reactions [FeFe]-hydrogenase model compounds; electrochemistry; spectroelectrochemistry; infrared spectroscopy; dithiolato-bridged diiron carbonyl compounds; ligand substitution reactions; coupled electron proton reactions
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MDPI and ACS Style

Tard, C.; Borg, S.J.; Fairhurst, S.A.; Pickett, C.J.; Best, S.P. Electronic Communication between Dithiolato-Bridged Diiron Carbonyl and S-Bridged Redox-Active Centres. Inorganics 2019, 7, 37.

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