Synthesis and Reactivity of Me2P(ZrCp2Cl)NAr, the First Iminozirconiophosphorane, a Masked Iminophosphide

Insertion of a phosphorus atom into zirconium–methyl bonds, and migration of a chlorine atom to the metal center—the reaction of the chloroiminophosphane ClPNAr (Ar = 2,4,6-tBu3C6H2) with the zirconocene [Cp2ZrMe2] occurring at −40 °C to give the metalated iminophosphorane 1 can be outlined in this way. Compound 1 reacts with nitriles RCN (R  Me, iPr, Ph) to give the unusual insertion products 2, and thus behaves as an iminophosphide; at room temperature 1 rearranges to the thermodynamically more stable aminophosphane 3.