Pentamethylcyclopentadienyl-rhodium and -iridium complexes. Part 32. Reactions of tri-µ-hydroxo-complexes with aniline and aliphatic amines

Abstract

The complexes [{M(C₅Me₅)}₂(OH)₃]OH (1, M = Rh; 2, M = Ir) react with aniline in the presence of PF₆^– or BF₄^– to give the µ-anilido-complexes [{M(C₅Me₅)}₂(µ-NHPh)(µ-OH)₂]⁺. Models show that the anilido-ligand sits rigidly in a pocket between the metal atoms and the n.m.r. spectra indicate there to be no rotation about the C–N bond. Primary alkylamines react with (1) to give tris(amine) complexes [Rh(C₅Me₅)(NH₂R)₃]²⁺(R = n-propyl or benzyl) which immediately dissociate in solution. Reasons for the differences in behaviour of the two types of amines are discussed.