dc.contributor.author |
Keidel, Anke |
dc.contributor.author |
López, Isidoro |
dc.contributor.author |
Staffa, Jana |
dc.contributor.author |
Kuhlmann, Uwe |
dc.contributor.author |
Bozoglian, Fernando |
dc.contributor.author |
Gimbert-Suriñach Carolina |
dc.contributor.author |
Benet-Bucholz, Jordi |
dc.contributor.author |
Hildebrandt, Peter |
dc.contributor.author |
Llobet, Antoni |
dc.date.accessioned |
2018-01-15T16:04:10Z |
dc.date.accessioned |
2018-02-15T10:27:26Z |
dc.date.available |
2018-01-15T16:04:10Z |
dc.date.available |
2018-02-15T10:27:26Z |
dc.date.issued |
2016 |
dc.identifier.uri |
http://hdl.handle.net/2072/226310 |
dc.identifier.uri |
http://hdl.handle.net/2072/305744 |
dc.language.iso |
eng |
dc.publisher |
Wiley |
dc.relation |
MINECO with FEDER Funds |
dc.relation |
Proyectos I+D+i - Retos 2013 |
dc.relation |
Severo Ochoa Excellence Accreditation 2014-2018 |
dc.relation |
PRO-H |
dc.relation.ispartof |
ChemSusChem Communications |
dc.rights |
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim |
dc.title |
Electrochemical and Resonance Raman Spectroscopic Studies of Water-Oxidizing Ruthenium-Terpyridyl-Bipyridyl Complexes |
dc.type |
info:eu-repo/semantics/article |
dc.relation.projectID |
CTQ2013-49075-R |
dc.relation.projectID |
SEV2013-0319 |
dc.relation.projectID |
CTQ2014-52974-REDC |
dc.identifier.doi |
https://dx.doi.org/10.1002/cssc.201601221 |
dc.rights.accessLevel |
info:eu-repo/semantics/openAccess |
dc.description.abstract |
The irreversible conversion of single-site water oxidation catalysts (WOC) into the more rugged catalysts structurally related to [(trpy)(5,5’-X2-bpy)RuIV(μ-O)RuIV(trpy)(O)(H2O)]4+ (X = H, 1-dn4+; X = F, 2-dn4+) represents a critical issue in developing active and durable WOC. In this work, the electrochemical and acid-base properties of 1-dn4+ and 2-dn4+ were evaluated. In-situ resonance Raman spectroscopy was employed to characterize species formed upon stoichiometric oxidation of single-site catalysts demonstrating the formation of high oxidation states mononuclear Ru=O and RuO-O complexes. Under turnover conditions, the dinuclear intermediates, 1-dn4+ and 2-dn4+, as well as the previously proposed [RuVI(trpy)(O)2(H2O)]2+ complex (32+) are formed. 32+ is a pivotal intermediate that provides access to the formation of dinuclear species. Single crystal X-ray diffraction analysis of the isolated complex [RuIV(O)(trpy)(5,5’-F2-bpy)]2+ reveals a clear elongation of the Ru-N bond located in the trans position to the oxo group, documenting the weakness of this bond which promotes the release of the bpy ligand and the subsequent formation of 32+. |