Synthesis and Characterization of [RuCl3(P-P)(H2O)] Complexes; P-P = Achiral or Chiral, Chelating Ditertiary Phosphine Ligands
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- 作者：Luis R. Dinelli ; Alzir A. Batista ; Karen Wohnrath ; Marcio P. de Araujo ; Salete L. Queiroz ; Marcos R. Bonfadini ; Glaucius Oliva ; Otaciro R. Nascimento ; Paul W. Cyr ; Kenneth S. MacFarlane ; and Brian R.
- 刊名：Inorganic Chemistry
- 出版年：1999
- 出版时间：November 15, 1999
- 年：1999
- 卷：38
- 期：23
- 页码：5341 - 5345
- 全文大小：87K
- 年卷期：v.38,no.23(November 15, 1999)
- ISSN：1520-510X
文摘
The reaction of the dinuclear [RuCl2(dppb)]2(
-dppb) (dppb = 1,4-bis(diphenylphosphino)butane) with Cl2 inMeOH for ~30 min at room temperature gives the bright-red solid mer-RuCl3(dppb)(H2O) (1); Cl2 treatment for~10 min affords the red-brown, mixed valence complex [RuCl(dppb)]2(-Cl)3 (2). Controlled bulk coulometricreduction 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 spectroscopictechniques [including electron spin resonance (ESR)], magnetic moments and cyclic voltammetry, and the structureof 1 was determined by X-ray diffraction. The structure shows that the aquo ligand forms hydrogen bonds withtwo cis-chlorine ligands of the neighboring molecule of the complex; this interaction gives rise to exchangecoupling between two Ru(III) centers that is reflected in the ESR spectrum. A species 3 analogous to 1 has beenobtained 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(-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.
-dppb) (dppb = 1,4-bis(diphenylphosphino)butane) with Cl2 inMeOH for ~30 min at room temperature gives the bright-red solid mer-RuCl3(dppb)(H2O) (1); Cl2 treatment for~10 min affords the red-brown, mixed valence complex [RuCl(dppb)]2(-Cl)3 (2). Controlled bulk coulometricreduction 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 spectroscopictechniques [including electron spin resonance (ESR)], magnetic moments and cyclic voltammetry, and the structureof 1 was determined by X-ray diffraction. The structure shows that the aquo ligand forms hydrogen bonds withtwo cis-chlorine ligands of the neighboring molecule of the complex; this interaction gives rise to exchangecoupling between two Ru(III) centers that is reflected in the ESR spectrum. A species 3 analogous to 1 has beenobtained 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(-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.