The synthesis of four new iridium(III) complexes mer-Ir ( This is a simplification of our previously reported procedure that involved preparation of a silver NHC complex prior to addition of [Ir(COD)Cl]2 in a 2-step, 1-pot reaction. The iridium complexes were isolated as a mixture of mer and fac isomers (in a 3.5:1 ratio for the benzyl compounds and a 5.5:1 ratio for the trimethylbenzyl compounds). The isomers could be separated by careful, repeated column chromatography on silica. The mer isomers were isolated in high yield (71 and 58%, respectively for mer-Ir(tfpi_Bn)3 and mer-Ir(tfpi_tmBn)3). In contrast to our previous work, the fac isomers could be isolated from these reactions. fac-Ir(tfpi_Bn)3 was obtained in 17% yield; however, it proved exceptionally difficult to purify fac-Ir(tfpi_tmBn)3 and only a small amount of material, corresponding to a 2% yield, was isolated, which limited its subsequent characterization. Attempts to promote acid-catalyzed mer-to-fac isomerization of mer-Ir(tfpi_tmBn)3 according to established procedures were not successful. All four iridium complexes exhibit a distorted octahedral environment about the iridium center. The bond lengths and angles are consistent with previously reported mer/fac-Ir(C^C)3 complexes (Table ).