A new PNP-pincer ligand 1 bearing neopentyl substituents reacted with [Ir(cod)(2)]BF4 to form hydridoiridacycle 3 via oxidative addition of a C-H bond of a neopentyl group to Ir-1. Addition of pi-acceptor ligands induced C-H reductive elimination to form cationic iridium(I) complexes 5 ligated by the pi-acceptor ligand. Although 3 did not give a benzene adduct, reaction of 3 with nitrobenzene or acetophenone afforded the C-H activated 7a or 8a.