Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Abstract

Cyclic PON, a first 16-electron triatomic ring consisting of two first-row elements, has been generated through 193 nm laser photolysis of OPN in cryogenic matrices. When the photolysis (365 nm) was performed in the presence of CO, OPN combines CO and furnishes an exotic acyclic molecule OPNCO. Upon the 193 nm laser irradiation, OPNCO dissociates mainly to OPN and CO with traces of PN and CO . The identification of cyclic PON and OPNCO with IR spectroscopy is supported by N-labeling experiments and quantum chemical calculations.

Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase

“…Traces of F 2 P(S)NCO (a) reforms by recombining the singlet thiophosphoryl nitrene F 2 P(S)N with CO in same matrix cages. Similar photolytic COassociation reactions have been previously observed for the phosphorus analogue of nitrous oxide (OPN + CO!OPNCO) [36] and phenylborylene (PhB + CO!PhBCO). [37]…”

Photolysis of PCl3/POCl3 with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

“…Alternately, the same oxyphosphinidene was reported to be generated via the generation of oxyphosphinidene from 266 nm photolysis of methoxydiazidophosphine, followed by 193 nm excitation . Furthermore, an elusive 16‐electron triatomic cyclic PON ring was generated through the photolysis of OPN in low temperature N 2 matrix . It is therefore obvious that the 193 nm photolysis can induce reactions, which are distinctive.…”

Frustrated Lewis Pair Stabilized Phosphoryl Nitride (NPO), a Mono Phosphorus Analogue of Nitrous Oxide (N2O)

“…X-ray diffraction analysis on a single crystal directly grown from a benzene/pentane solution after irradiation reveals the Cy3P-NPO-B(C6F5)3 structure (Figure 4C). The latter splitting originates from through space coupling of phosphorus to fluorine in B(C6F5)3 as only a doublet signal is observed in the 31 P{ 1 H, 19 F} NMR experiment. 42 The compound is thermally unstable and decomposes after one day at room temperature or by heating over night at 50 °C.…”

“…Phosphoryl nitride was first generated 10 years ago via the irradiation of explosive phosphoryl triazide (O=P(N3)3) [15][16][17] and characterized under cryogenic matric isolation conditions. [18][19] Phosphoryl nitride undergoes photochemically induced isomerizations to PNO and cyclic PON (Figure 1) and reversibly combines with carbon monoxide. [18][19] On the other hand, the phosphorus(III) isomer PON has been known since 1988 and was formed after photolysis of an O3/PN mixture diluted in solid argon under cryogenic matrix isolation conditions.…”

“…[18][19] Phosphoryl nitride undergoes photochemically induced isomerizations to PNO and cyclic PON (Figure 1) and reversibly combines with carbon monoxide. [18][19] On the other hand, the phosphorus(III) isomer PON has been known since 1988 and was formed after photolysis of an O3/PN mixture diluted in solid argon under cryogenic matrix isolation conditions. 20 Interestingly, NPO was not observed in this experiment.…”