Issue 7, 2015

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

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 ligands. Through an extensive investigation of redox-active ligands we revealed the most critical factors that facilitate or suppress 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 rational redox-leveling, i.e. the moderation of redox potentials of ligand-centred electron transfer processes, potentially leading to catalysts with low overpotential in multielectron activation processes.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
30 Mar 2015
Accepted
30 Apr 2015
First published
01 May 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 4109-4117

Author version available

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

G. Skara, B. Pinter, P. Geerlings and F. De Proft, Chem. Sci., 2015, 6, 4109 DOI: 10.1039/C5SC01140J

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