title: Oxidation state characterization of ruthenium 2-iminoquinone complexes through experimental and theoretical studies.
abstract: The synthesis of complexes [Ru(II)(trpy)(2-imino-4-tert-butylquinone)(Cl)](+) and [Ru(II)(trpy)(NIL)(OAc)](+) (where trpy = 2:2',6':2''-terpyridyl, NIL = 2-imino-4-tert-butylquinone, 2-imino-4-methylquinone, 2-iminoquinone, 2-imino-4-chloroquinone, 2-imino-5-chloroquinone, 2-imino-4,6-di-tert-butyl-N-phenyl-quinone, 2-imino-4,6-di-tert-butyl-N-(2'-trifluoromethylphenyl)-quinone) is reported. The oxidation states of these complexes, as well as the previously reported [Ru(III)(trpy)(2-iminosemiquinone)(Cl)](+) complex, are investigated by spectroscopic, electrochemical and theoretical methods resulting in the latter complex being reassigned as [Ru(II)(trpy)(2-iminoquinone)(Cl)](+). Evidence for the presence of two structural isomers was found for all complexes, and crystal structures for both isomers of the [Ru(II)(trpy)(2-imino-4-tert-butylquinone)(Cl)]ClO(4) complex are reported, as well as for the cis isomer of [Ru(II)(trpy)(2-imino-4,6-di-tert-butyl-N-phenyl-quinone)(OAc)]PF(6). Redox control is also demonstrated based on the Hammett parameters of the substituents on the 2-iminoquinone ligand.
authors.affiliation: Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000, USA.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Rochford
authors.forename: Ming-Kang
authors.initials: MK
authors.lastname: Tsai
authors.forename: David J
authors.initials: DJ
authors.lastname: Szalda
authors.forename: Julie L
authors.initials: JL
authors.lastname: Boyer
authors.forename: James T
authors.initials: JT
authors.lastname: Muckerman
authors.forename: Etsuko
authors.initials: E
authors.lastname: Fujita
mesh_terms: D003198:Computer Simulation; D018360:Crystallography, X-Ray; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D011809:Quinones / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D009942:Organometallic Compounds; D011809:Quinones; C116897:iminoquinone; D012428:Ruthenium