A series of new N-alkyl functionalised 6- and 7-membered expanded ring N-heterocyclic carbene (NHC) pro-ligands 3–6 and their corresponding complexes of rhodium(I) and iridium(I), [M(NHC)(COD)Cl] 7–14 and [M(NHC)(CO)₂Cl] 15–22 are described. The complexes have been characterised by ¹H and ¹³C{¹H} NMR, mass spectrometry, IR and X-ray diffraction. It is noted from X-ray diffraction studies that the N-alkyl substituents are found to orientate themselves away from the metal centre due to unfavourable steric interactions resulting in low percent buried volume (%V_bur) values in the solid state. The heterocycle ring size is also found to dictate the spatial orientation of the N-alkyl substituents in the neopentyl functionalised derivatives 10 and 14. The 7-membered derivative 14 allows for a conformational ‘twist’ of the heterocycle ring with the N-alkyl substituents adopting a mutually trans configuration with respect to each other, while the more rigid 6-membered system 10 does not allow for this conformational ‘twist’ and consequently the N-alkyl substituents adopt a mutually cis configuration. The σ-donor function of this new class of expanded ring NHC ligand has also been probed by measured IR stretching frequencies of the [M(NHC)(CO)₂Cl] complexes 15–22. A preliminary catalytic survey of the hydrogenation of functionalised alkenes with molecular hydrogen under mild conditions has also been undertaken with complex 10, affording an insight into the application of large ring NHC ancillary ligands bearing N-alkyl substituents in hydrogenation transformations.