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

13 April 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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.


Oxidative Addition
Bond Cleavage
Small Molecule Activation

Supplementary materials

Supporting Information
Synthesis and characterization of compounds, NMR spectra, crystallographic, and computational details. CCDC 2141957- 2141968 contain the supplementary crystallographic data for this paper.


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