title: Synthesis and characterization of ruthenium bis-bipyridine mono- and disulfinato complexes.
abstract: Reaction of cis-Ru(bpy)(2)Cl(2) with 1,2-benzenedithiol afforded a monosulfhydryl-monosulfinate complex, [Ru(bpy)(2)(S.SO(2))] (1). Complex 1 readily undergoes oxidation when treated with 30% H(2)O(2) and also upon exposure to atmospheric O(2) (rapidly in bright light) to afford the disulfinate complex, [Ru(bpy)(2)(SO(2.)SO(2))] (2). Complexes 1 and 2 were studied using various analytical techniques including elemental analysis, UV-vis, mass spectroscopy, NMR, IR spectroscopy, cyclic voltammetry, X-ray crystallography (for 2). Density functional theory computation was employed with extended charge decomposition and natural population analyses. The agreement between the observed electronic spectrum and that predicted by time dependent DFT, and between the observed infrared spectrum and that predicted by DFT, is truly exceptional. These molecules are relevant to the very unusual active site in the metalloenzyme nitrile hydratase.
authors.affiliation: Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario M3J 1P3, Canada.
authors.forename: Rowshan Ara
authors.initials: RA
authors.lastname: Begum
authors.forename: Abdiaziz A
authors.initials: AA
authors.lastname: Farah
authors.forename: Howard N
authors.initials: HN
authors.lastname: Hunter
authors.forename: A B P
authors.initials: AB
authors.lastname: Lever