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Synthesis and characterization of [RuCl3(P-P)(H2O)] complexes; P-P = achiral or chiral, chelating ditertiary phosphine ligands

TitleSynthesis and characterization of [RuCl3(P-P)(H2O)] complexes; P-P = achiral or chiral, chelating ditertiary phosphine ligands
Publication TypeJournal Article
Year of Publication1999
AuthorsDinelli, LR, Batista, AA, Wohnrath, K, de Araujo, MP, Queiroz, SL, Bonfadini, MR, Oliva, G, Nascimento, OR, Cyr, PW, Macfarlane, KS, James, BR
JournalInorganic Chemistry
Volume38
Pagination5341-5345
Date PublishedNov
Type of ArticleArticle
ISBN Number0020-1669
KeywordsASYMMETRIC HYDROGENATION, BINAP, CATALYSTS, COMPLEXES, CRYSTAL-STRUCTURE, DICARBOXYLATE COMPLEXES, GENERAL-SYNTHESIS, METAL-COMPLEXES, ruthenium, STRUCTURAL CHARACTERIZATION, UNSATURATED CARBOXYLIC-ACIDS
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.

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