Reaction of o-diethynylbenzene with transition metal-complexed primary phosphines gives in a single base-induced step stable phosphepine complexes as confirmed by X-ray data. At 75-80 es/entities/deg.gif">C these phosphepines undergo clean cheletropic elimination of naphthalene to give transient carbene-like phosphinidene complexes that can be trapped in high yield by alkenes, alkynes, and alcohols.