N-heterocyclic carbenes (NHCs) are cyclic carbenes bearing at least one α-amino substituent. Many NHC-metal complexes have been extensively used as catalysts for various applications. New imidazole and triazole based NHC complexes of rhodium and iridium have been synthesized and characterized using multinuclear NMR and x-ray diffraction studies. These iridium and rhodium complexes show excellent catalytic properties in the transfer hydrogenation reduction of ketones, imines, and alkenes. In addition, some rhodium complexes prove to be promising catalysts in selective hydrogenation, one pot synthesis of N-benzyl aniline, and in the cyclization reaction of 2-aminophenyl alcohol. The effect of metals, ligand electronics and steric properties, and ancillary phosphene ligands in their catalytic ability have been studied.