 Unlike other Rh(I) catalysts, the rhodium analogue of Wilkinson's catalyst RhCl(PHCy2)3 (Cy=cyclohexyl) behaves like the RhL2 and Rh(H)2L2 catalysts as a homogeneous species.In comparison to RhCl(PHCy2)3, the iridium analogue has reduced catalytic activity on the dehydrogenation of non sterically hindered amine-boranes, and increased activity on more sterically hindered substrates.Dehydrocoupling of primary diborazanes NH2R—BH2—NHR—BH3 can be catalyzed by via conversion to the metal-bound species MeNH—BH2 and subsequent polymerization/oligomerization.