Five- and Six-Coordinate Ruthenium(II) Complexes Containing the Bidentate Phosphane (−)-N,N-Bis(diphenylphosphanyl)-(S)-1-phenylethylamine [(S)-peap]: X-ray Crystal Structure of the First 16-Electron Ruthenium Complex Bearing a Four-Membered Ring [RuCl{κ2-P,P-(S)-peap}2][SbF6]·C2H4Cl2

✍ Scribed by Josefina Díez; M. Pilar Gamasa; José Gimeno; Yolanda Rodríguez; Santiago García-Granda

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 180 KB
• Volume: 2004
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200300755

✦ Synopsis

Abstract

The complex trans‐[RuCl~2~{κ^2^‐P,P‐(S)‐peap}~2~] (1) has been stereoselectively prepared by the treatment of a stoichiometric mixture of complex [RuCl~2~(DMSO)~4~] (DMSO = dimethyl sulfoxide) and (S)‐peap [(S)‐peap = (−)‐N,N‐bis(diphenylphosphanyl)‐(S)‐1‐phenylethylamine] in refluxing toluene. Irradiation of a dichloromethane solution of 1 with a UV lamp (400 W) at −15 °C affords the complex cis‐[RuCl~2~{κ^2^‐P,P‐(S)‐peap}~2~] (2). The thermodynamically stable trans isomer 1 has also been obtained by heating complex 2 in toluene. The reaction of 1 with AgSbF~6~ in dichloromethane yields the complex [RuCl{κ^2^‐P,P‐(S)‐peap}~2~][SbF~6~] (3), the first 16‐electron cationic ruthenium complex bearing a four‐membered chelate diphosphane ligand which has been fully characterized including its X‐ray crystal structure. The reaction of unsaturated derivative 3 with CO gives the six‐coordinate complex cis‐[RuCl(CO){κ^2^‐P,P‐(S)‐peap}~2~][SbF~6~] (4) in a stereoselective manner, which slowly transforms into trans‐[RuCl(CO){κ^2^‐P,P‐(S)‐peap}~2~][SbF~6~] (5) in a dichloromethane solution. The reaction of [RuCl{κ^2^‐P,P‐(S)‐peap}~2~][BF~4~] with 1‐phenyl‐2‐propyn‐1‐ol in 1,2‐dichloroethane (60 °C) affords the allenylidene derivative trans‐[RuCl(=C=C=CHPh){κ^2^‐P,P‐(S)‐peap}~2~][BF~4~] (6). The cis‐[Ru(acac){κ^2^‐P,P‐(S)‐peap}~2~][SbF~6~] (7) is prepared by reaction of 3 and Na[acac]. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)