Royal Society of Chemistry, Chemical Science, 7(6), p. 4109-4117
DOI: 10.1039/c5sc01140j
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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.