Reductive Elimination at Pb(II) Center of an (Amino)plumbylene‐Substituted Phosphaketene: New Pathway for Phosphinidene Synthesis

A stable (amino)plumbylene‐substituted phosphaketene 3 was synthesized by the successive reactions of PbCl(2) with two anionic reagents (lithium amidophosphine and NaPCO). Of particular interest, the thermal evolution of 3, at 80 °C, leads to the transient formation of corresponding amino‐ and phosphanylidene‐phosphaketenes (6 and 7), via a reductive elimination at the Pb(II) center forming new N−P and P−P bonds. Further evolution of 6 gives a new cyclic (amino)phosphanylidene phosphorane 4, which shows a unique reactivity as a phosphinidene. This result provides a new synthetic route to phosphinidenes, extending and facilitating further their access.