Design of Iron Coordination Complexes as Highly Active Homogenous Water Oxidation Catalysts by Deuteration of Oxidation-Sensitive Sites
dc.contributor.author
dc.date.accessioned
2019-05-07T12:08:11Z
dc.date.available
2019-05-07T12:08:11Z
dc.date.issued
2019
dc.identifier.issn
0002-7863
dc.identifier.uri
dc.description
Data de publicació online és 30 de novembbre de 2018, malgrat que apareix publicat en una revista del 2019
dc.description.abstract
The nature of the oxidizing species in water oxidation reactions with chemical oxidants catalyzed by α-[Fe(OTf)2(mcp)] (1α; mcp = N,N′-dimethyl-N,N′-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine, OTf = trifluoromethanesulfonate anion) and β-[Fe(OTf)2(mcp)] (1β) has been investigated. Mössbauer spectroscopy provides definitive evidence that 1α and 1β generate oxoiron(IV) species as the resting state. Decomposition paths of the catalysts have been investigated by identifying and quantifying ligand fragments that form upon degradation. This analysis correlates the water oxidation activity of 1α and 1β with stability against oxidative damage of the ligand via aliphatic C-H oxidation. The site of degradation and the relative stability against oxidative degradation are shown to be dependent on the topology of the catalyst. Furthermore, the mechanisms of catalyst degradation have been rationalized by computational analyses, which also explain why the topology of the catalyst enforces different oxidation-sensitive sites. This information has served in creating catalysts where sensitive C-H bonds have been replaced by C-D bonds. The deuterated analogues D4-α-[Fe(OTf)2(mcp)] (D4-1α), D4-β-[Fe(OTf)2(mcp)] (D4-1β), and D6-β-[Fe(OTf)2(mcp)] (D6-1β) were prepared, and their catalytic activity has been studied. D4-1α proves to be an extraordinarily active and efficient catalyst (up to 91% of O2 yield); it exhibits initial reaction rates identical with those of its protio analogue, but it is substantially more robust toward oxidative degradation and yields more than 3400 TON (n(O2)/n(Fe)). Altogether this evidences that the water oxidation catalytic activity is performed by a well-defined coordination complex and not by iron oxides formed after oxidative degradation of the ligands
dc.description.sponsorship
We acknowledge the Spanish Ministry of Science CTQ2015-70795-P (M. C.), CTQ2016-
80038-R (J. LL. F.), CTQ2014-59212-P (J. M. Lluis). We would like to thank the European
Commission for the ERC-CG-2014-648304 (J.Ll.-F) project
dc.format.extent
11 p.
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application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2015-70795-P/ES/GENERACION Y CARACTERIZACION DE ESPECIES DE HIERRO Y MANGANESO EN ALTOS ESTADOS DE OXIDACION, Y SU USO EN CATALISIS ASIMETRICA/
info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P/ES/SPIN STATE AND ENZYMATIC CATALYSIS BASED ON BOTTOM-UP COMPUTATIONAL DESIGN/
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Versió postprint del document publicat a: https://doi.org/10.1021/jacs.8b10211
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© Journal of the American Chemical Society, 2019, vol. 141, núm. 1, p. 123-133
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
Codolà Duch, Zoel Gamba, Ilaria Acuña-Parés, Ferran Casadevall, Carla Clémancey, Martin Latour, Jean Marc uis Luis, Josep Maria Lloret Fillol, Julio Costas Salgueiro, Miquel 2019 Design of Iron Coordination Complexes as Highly Active Homogenous Water Oxidation Catalysts by Deuteration of Oxidation-Sensitive Sites Journal of the American Chemical Society 141 1 123 133
dc.subject
dc.title
Design of Iron Coordination Complexes as Highly Active Homogenous Water Oxidation Catalysts by Deuteration of Oxidation-Sensitive Sites
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
029258
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5126