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[摘要]：Triplet difluorophosphoryl nitrene F2P(O)N (X(3)A") was generated on ArF excimer laser irradiation (lambda = 193 nm) of F2P(O)N-3 in solid argon matrix at 16 K, and characterized by its matrix IR, UV/Vis, and EPR spectra, in combination with DFT and CBS-QB3 calculations. On visible light irradiation (lambda > 420 nm) at 16 K F2P(O)N reacts with molecular nitrogen and some of the azide is regenerated. UV irradiation (lambda = 255 nm) of F2P(O)N (X(3)A") induced a Curtius-type rearrangement, but instead of a 1,3-fluorine shift, nitrogen migration to give F2PON is proposed to be the first step of the photoisomerization of F2P(O)N into F2PNO (difluoronitrosophosphine). Formation of novel F2PNO was confirmed with N-15- and O-18-enriched isotopomers by IR spectroscopy and DFT calculations. Theoretical calculations predict a rather long P-N bond of 1.922 angstrom [B3LYP/6-311 + G(3df)] and low bond-dissociation energy of 76.3 kJmol(-1) (CBS-QB3) for F2PNO. |
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