The synthesis of a novel family of cyclic push-pull carbenes, namely, azavinylidene phosphoranes, is described. The methodology is based on a formal [3+2] cycloaddition between terminal alkynes and phosphine-imines followed by an oxidation/deprotonation step. Carbenes 6, obtained by simple deprotonation, exhibit typical transient carbene reactivity like the intramolecular CH insertion reaction and a pronounced ambiphilic character exemplified by [2+1] cycloaddition with electron-poor methyl acrylate. Owing to the cyclic structure, carbenes 6 also exhibit an excellent coordination ability toward transition metals. Rh(I) complex 10 was obtained in excellent yield and was fully characterized by multinuclear NMR spectroscopy and X-ray crystallography. The corresponding Rh(I) -carbonyl complex was also prepared; this indicates that carbenes 6 belong to the strongest σ-donating ligands to date. DFT calculations confirmed the high σ-donation ability of 6 and their classification as push-pull carbenes with a relatively small singlet-triplet energy gap of 23.2-24.3 kcal mol(-1) .