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A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH

The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans,fac-{[RunX(bpea)]2(μ-bpp)}m+ (for X = Cl, n = II, m = 1, trans-RuII-Cl, 1+; for X = OH, n = III, m = 3, trans-RuIII-OH, 23+) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF6) with Ag+ generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(ii) to Ru(iii) to generate the corresponding dinuclear complex trans-RuIII-OH, 2(PF6)3. The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(iv) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O-O bond formation pathway

Support formSOLAR-H2(EU212508) and MICINN(CTQ2010-21497, Consolider Ingenio 2010 CSD2006-0003, CTQ2010-21532-C02-01 and CTQ2009-08328) is gratefully acknowledged

© Dalton Transactions, 2011, vol. 40, p. 3640-3646

Royal Society of Chemistry (RSC)

Manager: Ministerio de Ciencia e Innovación (Espanya)
Author: Mola i Marín, Joaquim
Dinoi, Chiara
Sala Román, Xavier
Rodríguez Pizarro, Montserrat
Romero García, Isabel
Parella Coll, Teodor
Fontrodona, Xavier
Llobet Dalmases, Antoni
Date: 2011 April 18
Abstract: The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans,fac-{[RunX(bpea)]2(μ-bpp)}m+ (for X = Cl, n = II, m = 1, trans-RuII-Cl, 1+; for X = OH, n = III, m = 3, trans-RuIII-OH, 23+) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF6) with Ag+ generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(ii) to Ru(iii) to generate the corresponding dinuclear complex trans-RuIII-OH, 2(PF6)3. The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(iv) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O-O bond formation pathway
Support formSOLAR-H2(EU212508) and MICINN(CTQ2010-21497, Consolider Ingenio 2010 CSD2006-0003, CTQ2010-21532-C02-01 and CTQ2009-08328) is gratefully acknowledged
Format: application/pdf
Citation: 018599
ISSN: 1477-9226 (versió paper)
1477-9234 (versió electrònica)
Document access: http://hdl.handle.net/10256/11723
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MICINN/PN 2011-2014/CTQ2010-21532-C02-01
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/C0DT00964D
Articles publicats (D-Q)
Is part of: © Dalton Transactions, 2011, vol. 40, p. 3640-3646
Rights: Tots els drets reservats
Subject: Ruthenium compounds
Electroquímica
Electrochemistry
Ruteni -- Compostos
Ruthenium compounds
Oxidació
Oxidation
Title: A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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