Small Molecule Activation on a Base‐stabilized Phosphinidene

Abstract

AbstractReduction of (NP)PCl2 (NP=phosphinoamidinate [PhC(NAr)(=NPPri2)]−) with KC8 affords the phosphinoamidinato‐supported phosphinidene (NP)P (9). Reaction of 9 with a N‐heterocyclic carbene (MeC(NMe))2C: results in the NHC‐adduct NHC→P−P(Pri2)=NC(Ph)=NAr featuring an iminophosphinyl group. Reactions of 9 with HBpin and H3SiPh led to the metathesis products (NP)Bpin and (NP)SiH2Ph, respectively, whereas with HPPh2 a base‐stabilized phosphido‐phosphinidene, the product of N−P and H−P bond metathesis, was obtained. Reaction of 9 with tetrachlorobenzaquinone results in oxidation of P(I) to P(III), accompanied by oxidation of the amidophosphine ligand into P(V). Addition of benzaldehyde to 9 results in a phospha‐Wittig reaction affording a product of P=P and C=O bond metathesis. Related reaction with phenylisocyanate results in a product of N−P(=O)Pri2 addition to the C=N bond of an intermediate iminophosphaalkene to produce a phosphinidene intramolecularly stabilized by a diaminocarbene.