Synthesis and Characterization of [RuCl3(P-P)(H2O)] Complexes; P-P = Achiral or Chiral, Chelating Ditertiary Phosphine Ligands

• DOI: 10.1021/ic990130c
• Publication Date: 2002-07-26T05:34:40Z
• Authors: Luis R. Dinelli; Alzir A. Batista; Karen Wohnrath; Marcio P. de Araujo; Salete L. Queiroz; Marcos R. Bonfadini; Glaucius Oliva; Otaciro R. Nascim...; Paul W. Cyr; Kenneth S. MacFar...; Brian R. James
• Keywords: Butane

The reaction of the dinuclear [RuCl2(dppb)]2(μ-dppb) (dppb = 1,4-bis(diphenylphosphino)butane) with Cl2 in MeOH for ∼30 min at room temperature gives bright-red solid mer-RuCl3(dppb)(H2O) (1); treatment ∼10 affords red-brown, mixed valence complex [RuCl(dppb)]2(μ-Cl)3 (2). Controlled bulk coulometric reduction 50% content a CH2Cl2 solution 1 also produces 2, formed by "RuCl2(dppb)" produced situ during electrolysis. Complexes and 2 were characterized spectroscopic techniques [including electron spin resonance (ESR)], magnetic moments cyclic voltammetry, structure was determined X-ray diffraction. shows that aquo ligand forms hydrogen bonds two cis-chlorine ligands neighboring molecule complex; this interaction rise to exchange coupling between Ru(III) centers is reflected ESR spectrum. A species 3 analogous has been obtained diop [diop (2R,3R)- or (2S,3S)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane], on using RuCl2(diop)(PPh3) [RuCl(diop)]2(μ-Cl)3 as precursors. RuCl3(P-P)L complexes (P-P dppb, diop; L dimethyl sulfoxide, MeOH) are readily synthesized from 3.