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Royal Society of Chemistry, Chemical Science, 7(6), p. 4109-4117

DOI: 10.1039/c5sc01140j

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Revealing the thermodynamic driving force for ligand-based reductions in quinoids; conceptual rules for designing redox active and non-innocent ligands

Journal article published in 2015 by Gabriella Skara, Balazs Pinter, Paul Geerlings, Frank De Proft
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

Metal and ligand-based reductions have been modeled in octahedral ruthenium complexes revealing metal-ligand interactions as the profound driving force for the redox-active behaviour of orthoquinoid-type of ligands. Through an extensive investigation of redox-active ligands we revealed the most critical factors that facilitate or supress redox-activity of ligands in metal complexes, from which basic rules for designing non-innocent/redox-active ligands can be put forward. These rules also allow the rational redox-leveling, i.e. moderating redox potentials of ligand-centred electron transfer processes potentially leading to catalysts with low overpotential in multielectron activation processes.