scrutinizing the noninnocence of quinone ligands in ruthenium complexes insights from structural,electronic,energy,an.审查的noninnocence醌钌配合物中配体的见解从结构、.pdfVIP

Article pubs.acs.org/IC Scrutinizing the Noninnocence of Quinone Ligands in Ruthenium Complexes: Insights from Structural, Electronic, Energy, and Effective Oxidation State Analyses Gabriella Skara,† Marti Gimferrer,‡ Frank De Proft,† Pedro Salvador,*,‡ and Balazs Pinter*,† †Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel (VUB), Pleinlaan 2, B-1050 Brussels, Belgium ‡Institut de Química Computacional i Catalisi (IQCC) i Department de Química, Universitat de Girona, 17071 Girona, Spaiǹ S *Supporting Information ABSTRACT: The most relevant manifestations of ligand noninnocence of quinone and bipyridine derivatives are thoroughly scrutinized and discussed through an extensive and systematic set of octahedral ruthenium complexes, [(en) z 2RuL] , in four oxidation states (z = +3, +2, +1, and 0). The characteristic structural deformation of ligands upon coordination/noninnocence is put into context with the underlying electronic structure of the complexes and its change upon reduction. In addition, by means of decomposing the corresponding reductions into electron transfer and structural relaxation subprocesses, the energetic contribution of these structural deformations to the redox energetics is revealed. The change of molecular electron density upon metal- and ligand-centered reductions is also visualized and shown to provide novel insights into the cor