A stable phosphanyl phosphaketene and its reactivity

Abstract

Sodium phosphaethynolate, Na(OCP), reacts with the bulky P-chloro-diazaphosphole yielding a phosphanyl phosphaketene, which is stable for weeks under an inert atmosphere in the solid state. This compound is best described as a tight ion pair with a remarkably long P–P bond distance (2.44 Å). In solution, this phosphaketene dimerizes under loss of CO to give 1,2,3-triphosphabicyclobutane identified by an X-ray diffraction study. As an intermediate, a five-membered heterocyclic diphosphene was trapped in a Diels–Alder reaction with 2,3-dimethylbutadiene. The formation of this intermediate in a hetero-Cope-rearrangement as well as dimerization/CO loss were computed with various DFT methods which allowed us to understand the reaction mechanisms.