Metal-Free N-H Bond Activation by Phospha-Wittig Reagents.

N-containing molecules are mostly derived from ammonia (NH 3 ). 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 NH 3 activation using ArP(PMe 3 ), affording for the first time isolable secondary aminophosphines ArP(H)NH 2 . DFT studies reveal that two molecules of NH 3 act in concert to facilitate an NH 3 for PMe 3 exchange. Furthermore, H 2 NR and HNR 2 activation is demonstrated.