title: Scrutinizing the Noninnocence of Quinone Ligands in Ruthenium Complexes: Insights from Structural, Electronic, Energy, and Effective Oxidation State Analyses.
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)2RuL](z), 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 corresponding redox processes. Moreover, the charge distribution of the π-subspace is straightforwardly examined and used as indicator of ligand noninnocence in the distinct oxidation states of the complexes. The aromatization/dearomatization processes of ligand backbones are also monitored using magnetic (NICS) and electronic (PDI) indicators of aromaticity, and the consequences to noninnocent behavior are discussed. Finally, the recently developed effective oxidation state (EOS) analysis is utilized, on the one hand, to test its applicability for complexes containing noninnocent ligands, and, on the other hand, to provide new insights into the magnitude of state mixings in the investigated complexes. The effect of ligand substitution, nature of donor atom, ligand frame modification on these manifestations, and measures is discussed in an intuitive and pedagogical manner.
authors: Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel (VUB) , Pleinlaan 2, B-1050 Brussels, Belgium.
authors: Gabriella
authors: G
authors: Skara
authors: Institut de Química Computacional i Catàlisi (IQCC) i Department de Química, Universitat de Girona , 17071 Girona, Spain.
authors: Marti
authors: M
authors: Gimferrer
authors: Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel (VUB) , Pleinlaan 2, B-1050 Brussels, Belgium.
authors: Frank
authors: F
authors: De Proft
authors: Institut de Química Computacional i Catàlisi (IQCC) i Department de Química, Universitat de Girona , 17071 Girona, Spain.
authors: Pedro
authors: P
authors: Salvador
authors: Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-UGent Alliance Research Group, Vrije Universiteit Brussel (VUB) , Pleinlaan 2, B-1050 Brussels, Belgium.
authors: Balazs
authors: B
authors: Pinter