Phosphenic isocyanate (O 2 PNCO): gas-phase generation, characterization, and photodecomposition reactions.

Phosphenic isocyanate (O 2 PNCO), a novel phosphorus-containing small molecule has been generated by thermolysis of a dioxaphospholane-based precursor. The characterization of O 2 PNCO with IR and UV-vis spectroscopy in solid N 2 and Ar matrices at 10 K is supported by the calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level of theory. Upon irradiation at 193 nm, O 2 PNCO decomposes yielding CO 2 , OPN, CO, ˙NO, and ˙PO, in which the possible formation of two exotic intermediates O 2 PN and OPNO in the triplet ground state has been proposed.