Oxo-bridge scenario behind single-site water-oxidation catalysts

Isidoro López, Somnath Maji, J. Benet-Buchholz, Antoni Llobet

Research output: Contribution to journalArticleResearchpeer-review

21 Citations (Scopus)

Abstract

© 2014 American Chemical Society. High-oxidation-state decay of mononuclear complexes [RuTB(H<inf>2</inf>O)]<sup>2+</sup> (X<sup>2+</sup>, where B = 2,2′-bpy or bpy for X = 1; B = 5,5′-F<inf>2</inf>-bpy for X = 2; B = 6,6′-F<inf>2</inf>-bpy for X = 3; T = 2,2′:6′,2″-terpyridine) oxidized with a large excess of Ce<sup>IV</sup> generates a manifold of polynuclear oxo-bridged complexes. These include the following complexes: (a) dinuclear [TB-Ru<sup>IV</sup>-O-Ru<sup>IV</sup>-(T)(O)OH<inf>2</inf>]<sup>2+</sup> (1-dn<sup>4+</sup>), [TB-Ru<sup>III</sup>-O-Ru<sup>III</sup>-T(MeCN)<inf>2</inf>]<sup>4+</sup> (1-dn-N<sup>4+</sup>), and {[Ru<sup>III</sup>(trpy)(bpy)]<inf>2</inf>(μ-O)}<sup>4+</sup> (1-dm<sup>4+</sup>); (b) trinuclear {[Ru<sup>III</sup>(trpy)(bpy)(μ-O)]<inf>2</inf>Ru<sup>IV</sup>(trpy)(H<inf>2</inf>O)}(ClO<inf>4</inf>)<inf>5</inf><sup>6+</sup> (1-tr<sup>6+</sup>) and {[Ru<sup>III</sup>(trpy)(bpy)(μ-O)]<inf>2</inf>Ru<sup>IV</sup>(pic)<inf>2</inf>}(ClO<inf>4</inf>)<inf>4</inf> (1-tr-P<sup>4+</sup>, where P is the 2-pyridinecarboxylate anion); and (c) tetranuclear [TB-Ru<sup>III</sup>-O-TRu<sup>IV</sup>(H<inf>2</inf>O)-O-TRu<sup>IV</sup>(H<inf>2</inf>O)-O-Ru<sup>III</sup>-TB]<sup>8+</sup> (1-tn<sup>8+</sup>), [TB-Ru<sup>III</sup>-O-TRu<sup>IV</sup>(AcO)-O-TRu<sup>IV</sup>(AcO)-O-Ru<sup>III</sup>-TB]<sup>6+</sup> (1-tn-Ac<sup>6+</sup>), and [TB-Ru<sup>II</sup>-O-TRu<sup>IV</sup>(MeCN)-O-TRu<sup>IV</sup>(MeCN)-O-Ru<sup>II</sup>-TB]<sup>6+</sup> (1-tn-N<sup>6+</sup>). These complexes have been characterized structurally by single-crystal X-ray diffraction analysis, and their structural properties were correlated with their electronic structures. Dinuclear complex 1-dm<sup>4+</sup> has been further characterized by spectroscopic and electrochemical techniques. Addition of excess Ce<sup>IV</sup> to 1-dm<sup>4+</sup> generates dioxygen in a catalytic manner. However, resonance Raman spectroscopy points to the in situ formation of 1-dn<sup>4+</sup> as the active species.
Original languageEnglish
Pages (from-to)658-666
JournalInorganic Chemistry
Volume54
Issue number2
DOIs
Publication statusPublished - 20 Jan 2015

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