@article {4520, title = {Synthesis and characterization of [RuCl3(P-P)(H2O)] complexes; P-P = achiral or chiral, chelating ditertiary phosphine ligands}, journal = {Inorganic Chemistry}, volume = {38}, number = {23}, year = {1999}, note = {ISI Document Delivery No.: 256ZATimes Cited: 29Cited Reference Count: 65}, month = {Nov}, pages = {5341-5345}, type = {Article}, abstract = {The reaction of the dinuclear [RuCl2(dppb)](2)(mu-dppb) (dppb = 1,4-bis(diphenylphosphino)butane) with Cl-2 in MeOH for similar to 30 min at room temperature gives the bright-red solid mer-RuCl3(dppb)(H2O) (1); Cl-2 treatment for similar to 10 min affords the red-brown, mixed valence complex [RuCl(dppb)](2)(mu-Cl)(3) (2). Controlled bulk coulometric reduction of 50\% of the content of a CH2Cl2 solution of 1 also produces 2, formed by the reaction of 1 with "RuCl2(dppb)" produced in situ during the electrolysis. Complexes 1 and 2 were characterized by spectroscopic techniques [including electron spin resonance (ESR)], magnetic moments and cyclic voltammetry, and the structure of 1 was determined by X-ray diffraction. The structure shows that the aquo ligand forms hydrogen bonds with two cis-chlorine ligands of the neighboring molecule of the complex; this interaction gives rise to exchange coupling between two Ru(III) centers that is reflected in the ESR spectrum. A species 3 analogous to 1 has been obtained with the diop ligand [diop = (2R,3R)- or (2S,3S)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane] , on using RuCl2(diop)(PPh3) or [RuCl(diop)](2)(mu-Cl)(3) as precursors. The RuCl3(P-P)L complexes (P-P = dppb, diop; L = dimethyl sulfoxide, MeOH) are readily synthesized from 1 or 3.}, keywords = {ASYMMETRIC HYDROGENATION, BINAP, CATALYSTS, COMPLEXES, CRYSTAL-STRUCTURE, DICARBOXYLATE COMPLEXES, GENERAL-SYNTHESIS, METAL-COMPLEXES, ruthenium, STRUCTURAL CHARACTERIZATION, UNSATURATED CARBOXYLIC-ACIDS}, isbn = {0020-1669}, url = {://000083755300020}, author = {Dinelli, L. R. and Batista, A. A. and Wohnrath, K. and de Araujo, M. P. and Queiroz, S. L. and Bonfadini, M. R. and Oliva, G. and Nascimento, O. R. and Cyr, P. W. and Macfarlane, K. S. and James, Brian R.} }