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Hydrogenase Biomimetics with Redox-Active Ligands: Synthesis, Structure, and Electrocatalytic Studies on [Fe2(CO)42-dppn)(µ-edt)] (edt = Ethanedithiolate; dppn = 1,8-bis(Diphenylphosphino)Naphthalene)

1
Department of Chemistry, King’s College London, Britannia House, 7 Trinity Street, London SE1 1DB, UK
2
Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh
3
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
4
Department of Chemistry, University of North Texas, 1155 Union Circle, Box 305070, Denton, TX 76203, USA
*
Authors to whom correspondence should be addressed.
Inorganics 2018, 6(4), 122; https://doi.org/10.3390/inorganics6040122
Received: 28 August 2018 / Revised: 5 November 2018 / Accepted: 9 November 2018 / Published: 20 November 2018
(This article belongs to the Special Issue Binuclear Complexes)
Addition of the bulky redox-active diphosphine 1,8-bis(diphenylphosphino)naphthalene (dppn) to [Fe2(CO)6(µ-edt)] (1) (edt = 1,2-ethanedithiolate) affords [Fe2(CO)42-dppn)(µ-edt)] (3) as the major product, together with small amounts of a P–C bond cleavage product [Fe2(CO)51-PPh2(1-C10H7)}(µ-edt)] (2). The redox properties of 3 have been examined by cyclic voltammetry and it has been tested as a proton-reduction catalyst. It undergoes a reversible reduction at E1/2 = −2.18 V and exhibits two overlapping reversible oxidations at E1/2 = −0.08 V and E1/2 = 0.04 V. DFT calculations show that while the Highest Occupied Molecular Orbital (HOMO) is metal-centred (Fe–Fe σ-bonding), the Lowest Unoccupied Molecular Orbital (LUMO) is primarily ligand-based, but also contains an antibonding Fe–Fe contribution, highlighting the redox-active nature of the diphosphine. It is readily protonated upon addition of strong acids and catalyzes the electrochemical reduction of protons at Ep = −2.00 V in the presence of CF3CO2H. The catalytic current indicates that it is one of the most efficient diiron electrocatalysts for the reduction of protons, albeit operating at quite a negative potential. View Full-Text
Keywords: hydrogenase biomimetics; dithiolate; proton-reduction; dppn; redox-active hydrogenase biomimetics; dithiolate; proton-reduction; dppn; redox-active
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Ghosh, S.; Rana, S.; Hollingsworth, N.; Richmond, M.G.; Kabir, S.E.; Hogarth, G. Hydrogenase Biomimetics with Redox-Active Ligands: Synthesis, Structure, and Electrocatalytic Studies on [Fe2(CO)42-dppn)(µ-edt)] (edt = Ethanedithiolate; dppn = 1,8-bis(Diphenylphosphino)Naphthalene). Inorganics 2018, 6, 122.

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