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[FeFe]-hydrogenase synthetic mimics based on peri-substituted dichalcogenides

[FeFe]-hydrogenase synthetic mimics based on peri-substituted dichalcogenides
[FeFe]-hydrogenase synthetic mimics based on peri-substituted dichalcogenides
Eight dithiolato-, diselenolato-, and mixed S,Se-Fe-2(CO)(6) complexes based on pen-substituted naphthalene and phenanthrene dichalcogenides are prepared by oxidative insertion of Fe-3(CO)(12) into the dichalcogen bonds of 2,7-dimethoxynaphtho[1,8cd][1,2]dithiole, three naphtho[1,8-cd][1,2]diselenoles, two naphtho[1,8-cd][1,2]thiaselenoles, phenanthro[1,10-cd][1,2]dithiole, and phenanthro[1,10-cd] [1,2]diselenole. Complexes are characterized by H-1, C-13 NMR, UV/vis, and IR spectroscopy and by X-ray analysis. The effect of replacing sulfur with selenium, incorporating electron-donating groups (2,7-di-ten-butyl, 2,7-climethoxy) on the naphthalene ring system, and changing the degree of conjugation in the aromatic backbone (naphthalene vs phenanthrene) on the reduction potential is evaluated by cyclic voltammetry. The electrocatalytic activity of these [FeFe]-hydrogenase synthetic mimics for proton reduction in the presence of increasing concentrations of p-TsOH is investigated. Diselenolate-based [FeFe]-complexes show enhanced catalytic activity for proton reduction compared with their sulfur congeners
0276-7333
4449-4460
Figliola, Carlotta
43cbb9f9-484e-4f2e-89ac-9b3501b0ba99
Male, Louise
89b88c4f-2308-4b94-8f3a-2dc537a66533
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horswell, Sarah L.
f5b96be6-f19b-40c8-84d7-dc1ff59c1434
Grainger, Richard S.
2361f475-1635-4240-ae44-dcb1ebaaaf52
Figliola, Carlotta
43cbb9f9-484e-4f2e-89ac-9b3501b0ba99
Male, Louise
89b88c4f-2308-4b94-8f3a-2dc537a66533
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horswell, Sarah L.
f5b96be6-f19b-40c8-84d7-dc1ff59c1434
Grainger, Richard S.
2361f475-1635-4240-ae44-dcb1ebaaaf52

Figliola, Carlotta, Male, Louise, Horton, Peter N., Pitak, Mateusz B., Coles, Simon J., Horswell, Sarah L. and Grainger, Richard S. (2014) [FeFe]-hydrogenase synthetic mimics based on peri-substituted dichalcogenides. Organometallics, 33 (17), 4449-4460. (doi:10.1021/om500683p).

Record type: Article

Abstract

Eight dithiolato-, diselenolato-, and mixed S,Se-Fe-2(CO)(6) complexes based on pen-substituted naphthalene and phenanthrene dichalcogenides are prepared by oxidative insertion of Fe-3(CO)(12) into the dichalcogen bonds of 2,7-dimethoxynaphtho[1,8cd][1,2]dithiole, three naphtho[1,8-cd][1,2]diselenoles, two naphtho[1,8-cd][1,2]thiaselenoles, phenanthro[1,10-cd][1,2]dithiole, and phenanthro[1,10-cd] [1,2]diselenole. Complexes are characterized by H-1, C-13 NMR, UV/vis, and IR spectroscopy and by X-ray analysis. The effect of replacing sulfur with selenium, incorporating electron-donating groups (2,7-di-ten-butyl, 2,7-climethoxy) on the naphthalene ring system, and changing the degree of conjugation in the aromatic backbone (naphthalene vs phenanthrene) on the reduction potential is evaluated by cyclic voltammetry. The electrocatalytic activity of these [FeFe]-hydrogenase synthetic mimics for proton reduction in the presence of increasing concentrations of p-TsOH is investigated. Diselenolate-based [FeFe]-complexes show enhanced catalytic activity for proton reduction compared with their sulfur congeners

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Published date: 8 September 2014
Organisations: Chemistry

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Local EPrints ID: 371987
URI: http://eprints.soton.ac.uk/id/eprint/371987
ISSN: 0276-7333
PURE UUID: 1557980c-6769-476c-977a-f6a00c2273ed
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for Mateusz B. Pitak: ORCID iD orcid.org/0000-0002-3680-7100
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 24 Nov 2014 11:09
Last modified: 18 Feb 2021 16:54

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Contributors

Author: Carlotta Figliola
Author: Louise Male
Author: Peter N. Horton ORCID iD
Author: Mateusz B. Pitak ORCID iD
Author: Simon J. Coles ORCID iD
Author: Sarah L. Horswell
Author: Richard S. Grainger

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