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Electrochemical and Resonance Raman Spectroscopic Studies of Water-Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes
Citation key CSSC:CSSC201601221
Author Keidel, Anke and López, Isidoro and Staffa, Jana and Kuhlmann, Uwe and Bozoglian, Fernando and Gimbert-Suriñach, Carolina and Benet-Buchholz, Jordi and Hildebrandt, Peter and Llobet, Antoni
Pages n/a–n/a
Year 2016
ISSN 1864-564X
DOI 10.1002/cssc.201601221
Journal ChemSusChem
Abstract The irreversible conversion of single-site water-oxidation catalysts (WOC) into 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+; bpy=2,2′-bipyridine; trpy=2,2′:6′,2“-terpyridine) represents a critical issue in the development of active and durable WOCs. 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 the species formed upon the stoichiometric oxidation of the single-site catalysts and demonstrated the formation of high-oxidation-state 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. Complex 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 trans to the oxido ligand that documents the weakness of this bond, which promotes the release of the bpy ligand and the subsequent formation of 32+.
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