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

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