Rhodium and Iridium Complexes of Abnormal N-Heterocyclic Carbenes Derived from Imidazo[1,2-a]pyridine

Rhodium and iridium complexes of a new type of abnormal N-heterocyclic carbenes (NHCs) derived from imidazo[1,2-a]pyridiniums have been prepared via silver transmetalation, where metalation can be directed to either the C-2 or the C-3 position of imidazo[1,2-a]pyridine ring provided that the other position is appropriately blocked. The donating abilities of these new NHC ligands have been assessed from the average CO stretching frequencies of their corresponding iridium dicarbonyl complexes. By varying the N-alkyl groups or fusing the pyridine moiety with an aromatic ring, electronic effects of abnormal NHCs of this type can be readily tuned to match the extremely donating imidazole-derived abnormal NHCs or the relatively less donating normal NHCs (imidazolin-2-ylidenes). Both VT NMR studies and CO stretching frequency values strongly support the π-accepting ability of an abnormal NHC derived from imidazo[1,2-a]quinoline.