The synthesis, structure determination and oxidative stability of novel Rh–NHC complexes which feature pyridine-derived ligands have been described. All complexes described herein were synthesized from common dinuclear precursors of general structure [Rh(NHC)(L)Cl]2, where L is a monodentate olefin. We demonstrate that the use of these precursors is critical for the formation of all complexes since related cyclooctadiene containing precursors ([Rh(NHC)(COD)Cl]) were completely unreactive under identical conditions. We further demonstrate that complexes with the general formula [Rh(NHC)(olefin)(Py)Cl] or ([Rh(NHC)(BiPy/Phen)Cl]) are extremely sensitive to oxygen, reacting initially to give an adduct with dioxygen, and then decomposing further. The series of compounds and their oxidation products gave a remarkable range of colours which may be useful in the preparation of colourometric oxygen sensors.