Ghosh, S;
Hollingsworth, N;
Warren, M;
Holt, KB;
Hogarth, G;
(2017)
Electrocatalytic proton reduction by [Fe(CO)2(κ2-dppv)(κ1-SAr)2] (dppv = cis-1,2-bis(diphenylphosphino)ethylene; Ar = C6F5, C6H5, C6H4CH3-p).
Polyhedron
, 137
pp. 140-146.
10.1016/j.poly.2017.08.008.
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Abstract
Electrocatalytic reduction of protons to hydrogen by mononuclear iron complexes which are developed as models of the distal iron center of [FeFe]-hydrogenase active site are described. A series of iron(II) bis(thiolate) complexes [Fe(CO) 2 (κ 2 -dppv)(κ 1 -SAr) 2 ] (1, Ar = C 6 F 5 ; 2, Ar = C 6 H 4 ; 3, Ar = C 6 H 4 CH 3 -p; dppv = cis-1,2-bis(diphenylphosphino)ethylene) have been prepared from direct reactions between the corresponding hexacarbonyl [Fe 2 (CO) 6 (μ-SAr) 2 ] and dppv at elevated temperatures. Structurally they are similar being coordinated by a chelating dppv, two carbonyls and two thiolate ligands bonded in an all cis-arrangement. Solution spectroscopic data indicate that they exist in two isomeric forms in solution. All reversibly protonate at sulphur atom(s) upon addition of HBF 4 ·Et 2 O and lose a thiolate ligand as thiol. They show a common quasi-reversible reductive feature (attributed to the Fe II /Fe I couple) in their CVs in addition to other redox responses and are able to catalyze reduction of protons to hydrogen at their Fe(I) oxidation state in presence of HBF 4 ·Et 2 O. Complex 1 is the most efficient catalyst and catalyzes proton reduction at ca. −1.5 V showing i cat /i p ≥46 in the presence of ten equivalents of HBF 4 ·Et 2 O.
| Type: | Article |
|---|---|
| Title: | Electrocatalytic proton reduction by [Fe(CO)2(κ2-dppv)(κ1-SAr)2] (dppv = cis-1,2-bis(diphenylphosphino)ethylene; Ar = C6F5, C6H5, C6H4CH3-p) |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/j.poly.2017.08.008 |
| Publisher version: | https://doi.org/10.1016/j.poly.2017.08.008 |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| Keywords: | Iron(II) complexes; Thiolate; Diphosphine; Hydrogenase biomimics; Electrocatalysis |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1575448 |
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