iPr2N–PFe(CO)4 in Olefinic Solvents: A Reservoir of a Transient Phosphinidene Complex Capable of Substrate Hopping

The phosphinidene complex iPr2N–PFe­(CO)4 was prepared as a storable phosphirane solution from Collman’s reagent and iPr2NPCl2 in the olefins 1-pentene and 1-hexene. The carbene-like reagent is able to hop under very mild conditions (>−25 °C) from one olefin to another and to alkynes to give the more stable phosphirenes that likewise display dynamic covalent behavior. The olefinic solutions are effective reservoirs for the highly reactive phosphinidene complex, as is illustrated in its N–H and O–H insertion reactions with amines, alcohols, and carboxylic acids and in its P–C bond formation with Grignard reagents.