Complexes [AuCl{C(NHR)(NHPy-2)}] (Py-2 = 2-pyridyl; R = Me, ^tBu, ⁿBu, ⁱPr, ⁿheptyl) have been prepared in a modular way from [AuCl(CNPy-2)]. The carbene moiety has a hydrogen-bond supported heterocyclic structure similar to the nitrogen heterocyclic carbenes in the solid state, and in CH₂Cl₂ or acetone solution, which is open in the presence of MeOH. The compounds are good catalysts for the skeletal rearrangement of enynes, and for the methoxycyclization of enynes. In contrast, the complexes [AuCl{C(NHR)(NHPy-4)}] are scarcely active due to the blocking effect of the coordination position required for the catalysis by the nitrogen of the NHPy-4 group.