title: {RuNO}(6)vs. co-ligand oxidation: two non-innocent groups in one ruthenium nitrosyl complex.
abstract: Recently, a new {RuNO}(6) complex, [Ru(L)(PPh3)(NO)(Cl)](2+) (where L = 1-phenyl-1-(pyridin-2-yl)-2-(pyridin-2-ylmethylene)hydrazine), was reported which exhibits a one-electron quasireversible oxidation. The oxidized product, [Ru(L)(PPh3)(NO)(Cl)](3+), was isolated and proposed to be a highly unusual {RuNO}(5) complex. In this paper, we investigate the electronic structure of both of these ruthenium complexes by DFT calculations and find that the oxidized species is best described as a {RuNO}(6) complex with a co-ligand radical. [Ru(L)(PPh3)(NO)(Cl)](2+) is therefore oxidized to [Ru(L(+˙))(PPh3)(NO)(Cl)](3+), i.e. this is an interesting example of a complex with two non-innocent ligands simultaneously bound to a ruthenium center.
authors.affiliation: Department of Chemistry and Department of Biophysics, University of Michigan, 930 North University Ave., Ann Arbor, MI 48109, USA. lehnertn@umich.edu.
authors.forename: Ashley B
authors.initials: AB
authors.lastname: McQuarters
authors.forename: Nicolai
authors.initials: N
authors.lastname: Lehnert