Three different reaction procedures for the coordination of IV-n-butyl-Ar-(2-pyridylmethyl)imidazolium salt have produced new N-heterocyclic complexes of Rh and Ir. The direct reaction of the imidazolium salt with [IrCl(cod)](2) provides a NK-Ir-III complex, while transmetalation from a silver-NHC complex and deprotonation with NEt3 give new NHC complexes of M(I) and M(III) when reacting with [MCI(cod)](2) or [MCI(coe)(2)](2) (M = Rh, Ir). The crystal structures of the biscarbene Rh(III) and Ir(III) complexes are described. The catalytic properties of the compounds obtained have been tested in the hydrosilylation of acetylenes, the cyclization of acetylenic carboxylic acids, and hydrogen transfer to ketones.