Photochemistry of phosphenic chloride (ClPO 2 ): isomerization with chlorine metaphosphite (ClOPO) and reduction by carbon monoxide.

Phosphenic chloride (ClPO 2 ) is an elusive congener of nitryl chloride (ClNO 2 ). By high-vacuum flash pyrolysis of 2-chloro-1,3,2-dioxaphospholane in the gas phase, ClPO 2 has been efficiently generated and subsequently isolated in cryogenic N 2 , Ar, and CO matrices (10 K) for a first time study on its photochemistry. Upon 193 nm laser irradiation, ClPO 2 isomerizes to the novel chlorine metaphosphite (ClOPO) by initial cleavage of the Cl-P bond (→ ˙Cl + ˙PO 2 ) with subsequent Cl-O bond formation inside the N 2 and Ar matrix cages. The reverse transformation becomes feasible under further irradiation at 266 nm. This photochemistry is consistent with the observed absorptions of ClPO 2 and ClOPO at 207 and 250 nm, respectively. When the photolysis was performed in solid CO ice, no isomerization occurs due to CO-trapping of the initially generated ˙Cl atoms by forming caged radical pair ClCO˙⋯˙PO 2 . Concomitantly, photolytic reduction of ClPO 2 to ClPO by CO has been observed, yielding a weakly bonded molecular complex consisting of ClPO and CO 2 bonded through short intermolecular C⋯O contact (2.910 Å). The characterization of ClPO, ClPO 2 , ClOPO, and the molecular complexes of ClPO 2 -CO and ClPO-CO 2 using matrix-isolation IR and UV-vis spectroscopy is supported by the theoretical calculations at the B3LYP/6-311 + G(3df) level, and the photochemistry of ClPO 2 is also compared with the revisited photochemistry of ClNO 2 in the N 2 -matrix.