1,10-Phenanthroline and 2,2′-bipyridyl complexes of rhodium(III)

Abstract

The preparation of cis-[Rh(aa)₂Cl₂]⁺(aa = 2,2′-bipyridyl or 1,10-phenanthroline) has been re-examined and shown to be catalytic. The preparation and characterisation of cis-[Rh(aa)₂X₂]ⁿ⁺(X = I^–, CN^–, H₂O, and NH₃) and cis-[Rh(aa)₂ClY]^m+(Y = H₂O, NH₃, pyridine, and NO₂^–) is described and the possible mechanisms of base hydrolysis and of substitution by cyanide and by iodide into cis-[Rh(aa)₂Cl₂]⁺ are discussed; the effect of dioxygen on these substitutions is also discussed. The resolution of cis-[M(aa)₂Cl₂]⁺(M = Rh or Ir) into optical isomers is described and their stability is discussed. A convenient catalytic preparation of [Rh(aa)₃]³⁺ is given.