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Understanding Electronic Ligand Perturbation over Successive Metal-Based Redox Potentials in Mononuclear Ruthenium–Aqua Complexes

A family of new ruthenium complexes containing a combination of polypyridyl and carbene ligands has been prepared and characterized from structural, spectroscopic, and redox viewpoints both experimentally and computationally. Interestingly, a correlation between ΔE1/2, defined as the difference between E1/2(RuIV/III) and E1/2(RuIII/II), and the activity and selectivity of some catalytic oxidation processes has been clearly established. A density functional theory study on the synthesized species has been carried out revealing a correlation between the number of carbene ligands and ΔE1/2, and consequently with the RuIII disproportionation. The reactivity of these complexes has been tested with regard to the electrocatalytic oxidation of benzyl alcohol.

Support from MINECO (CTQ2010-21497, CTQ2011-26440, CTQ2010-21532-C02-01, CTQ2009-08328, and CTQ2011-23121), “Torres y Quevedo” contract (X.S.) and Consolider Ingenio 2010 (CSD2006-0003) are gratefully acknowledged

© ChemPlusChem, 2013, vol. 78, núm. 3, p. 235 – 243

Wiley-VCH Verlag

Manager: Ministerio de Economía y Competitividad (Espanya)
Ministerio de Ciencia e Innovación (Espanya)
Author: Vaquer, Lydia
Miró, Pere
Sala Román, Xavier
Bozoglian, Fernando
Masllorens i Llinàs, Ester
Benet Buchholz, Jordi
Fontrodona, Xavier
Parella Coll, Teodor
Romero García, Isabel
Roglans i Ribas, Anna
Rodríguez Pizarro, Montserrat
Bo, Carles
Llobet Dalmases, Antoni
Date: 2013 March
Abstract: A family of new ruthenium complexes containing a combination of polypyridyl and carbene ligands has been prepared and characterized from structural, spectroscopic, and redox viewpoints both experimentally and computationally. Interestingly, a correlation between ΔE1/2, defined as the difference between E1/2(RuIV/III) and E1/2(RuIII/II), and the activity and selectivity of some catalytic oxidation processes has been clearly established. A density functional theory study on the synthesized species has been carried out revealing a correlation between the number of carbene ligands and ΔE1/2, and consequently with the RuIII disproportionation. The reactivity of these complexes has been tested with regard to the electrocatalytic oxidation of benzyl alcohol.
Support from MINECO (CTQ2010-21497, CTQ2011-26440, CTQ2010-21532-C02-01, CTQ2009-08328, and CTQ2011-23121), “Torres y Quevedo” contract (X.S.) and Consolider Ingenio 2010 (CSD2006-0003) are gratefully acknowledged
Format: application/pdf
Citation: 018608
ISSN: 2192-6506
Document access: http://hdl.handle.net/10256/13700
Language: eng
Publisher: Wiley-VCH Verlag
Collection: MINECO/PN 2011-2013/CTQ2010-21497
MICINN/PN 2011-2014/CTQ2010-21532-C02-01
MICINN/PN 2012-2014/CTQ2011-23121
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/cplu.201200268
Articles publicats (D-Q)
Is part of: © ChemPlusChem, 2013, vol. 78, núm. 3, p. 235 – 243
Rights: Tots els drets reservats
Subject: Ruteni -- Compostos
Ruthenium compounds
Funcional de densitat, Teoria del
Density functionals
Title: Understanding Electronic Ligand Perturbation over Successive Metal-Based Redox Potentials in Mononuclear Ruthenium–Aqua Complexes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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