Oxidative addition of chlorinated solvents (e.g. CH2Cl2 and CHCl3) with rhodium(I) complexes; crystal structure of mer-[Rh(py)3(CH2Cl)Cl2]

Abstract

Common chlorinated solvents (e.g. CH₂Cl₂ and CHCl₃) readily reacted with [Rh₂(C₈H₁₄)₄(µ-Cl)₂] (C₈H₁₄ = cyclooctene), in the presence of a monodentate, nitrogen donor ligand (L = py or 4-Bu^tpy), to give the oxidative addition product [RhL₃RCl₂] (R = CH₂Cl, CHCl₂ or CH₂Ph) which for R = CH₂Cl and CH₂Ph has been shown by X-ray analysis to adopt the mer configuration. NMR Spectroscopic measurements (¹³C and ¹⁵N) in solution were consistent with this configuration, although these NMR data cannot unambiguously distinguish between the mer and fac isomers.