Metal-free NH-oxidative addition at phospha-Wittig reagents

N-containing molecules are mostly derived from ammonia (NH3). Ammonia activation has been demonstrated for single transition metal centers as well as for low-valent main group species. Phosphinidenes, mono-valent phosphorus species, can be stabilized by phosphines, giving so-called phosphanylidenephosphoranes of the type RP(PR’3). We demonstrate the facile, metal-free NH3 activation using ArP(PMe3), affording for the first time isolable secondary aminophosphines ArP(H)NH2 through oxidative addition at a phosphinidenoid P atom. DFT studies reveal that two molecules of NH3 act in concert to facilitate an NH3 for PMe3 exchange. Furthermore, H2NR and HNR2 activation is demonstrated.