Ligand Exchange and Redox Processes in Iridium Triazolylidene Complexes Relevant to Catalytic Water Oxidation

DC FieldValueLanguage
dc.contributor.authorPetronilho, Ana-
dc.contributor.authorLlobet, Antoni-
dc.contributor.authorAlbrecht, Martin-
dc.date.accessioned2015-06-05T15:40:26Z-
dc.date.available2015-11-21T04:00:09Z-
dc.date.copyright2014 American Chemical Societyen
dc.date.issued2014-11-21-
dc.identifier.citationInorganic Chemistryen
dc.identifier.urihttp://hdl.handle.net/10197/6600-
dc.description.abstractIridium(III) complexes containing a bidentate spectator ligand have emerged as powerful catalyst precursors for water oxidation. Here we investigate the initial steps of the transformation at the iridium center when using complex [IrCp*(pyr-trz)Cl] 1 (Cp* = pentamethylcyclopentadienyl, pyr-trz = 4-(2-pyridyl)-1,2,3-triazol-5-ylidene), a potent water oxidation catalyst precursor. Ligand exchange with water is facile and is reversed in the presence of chloride ions, while MeCN substitution is effective only from the corresponding aqua complex. A pKa of 8.3 for the aqua complex was determined, which is in agreement with strong electron donation from the triazolylidene ligand that is comparable to aryl anions. Evaluation of the pH-dependent oxidation process in aqueous media reveals two regimes (pH 4–8.5 and above pH 10.5) where proton-coupled electron transfer processes occur. These investigations will help to further optimize water oxidation catalysts and indicate that MeCN as a cosolvent has adverse effects for initiating water coordination in the oxidation process.en
dc.description.sponsorshipEuropean Research Councilen
dc.description.sponsorshipScience Foundation Irelanden
dc.language.isoenen
dc.publisherAmerican Chemical Societyen
dc.rightsThis document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, copyright © American Chemical Society after peer review. To access the final edited and published work, see http://pubs.acs.org/doi/abs/10.1021/ic501894u.en
dc.subjectTriazolylidene iridium complexesen
dc.subjectCatalysisen
dc.subjectOxidation potentialen
dc.titleLigand Exchange and Redox Processes in Iridium Triazolylidene Complexes Relevant to Catalytic Water Oxidationen
dc.typeJournal Articleen
dc.statusPeer revieweden
dc.identifier.volume53en
dc.identifier.issue24en
dc.identifier.startpage12896en
dc.identifier.endpage12901en
dc.identifier.doi10.1021/ic501894u-
dc.neeo.contributorPetronilho|Ana|aut|-
dc.neeo.contributorLlobet|Antoni|aut|-
dc.neeo.contributorAlbrecht|Martin|aut|-
dc.description.othersponsorshipSpanish Ministry of Economy and Competitivenessen
dc.date.updated2015-05-26-
item.grantfulltextopen-
item.fulltextWith Fulltext-
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