Preparation and Characterization of P₂ BCh Ring Systems (Ch=S, Se) and Their Reactivity with N-Heterocyclic Carbenes

Four-membered rings with a P₂ BCh core (Ch=S, Se) have been synthesized by the reaction of phosphinidene chalcogenide (Ar*P=Ch) and phosphaborene (Mes*P=BNR₂ ). The mechanistic pathways towards these rings are explained by detailed computational work that confirmed the preference for the formation of P-P, not P-B, bonded systems, which seems counterintuitive given that both phosphorus atoms contain bulky ligands. The reactivity of the newly synthesized heterocycles, as well as that of the known (RPCh)_n rings (n=2, 3), was probed by the addition of N-heterocyclic carbenes, which revealed that all investigated compounds can act as sources of low-coordinate phosphorus species.