The phenylselenyl radical and its reaction with molecular oxygen

Abstract

The current study focuses on the generation, identification, and characterization of the phenylselenyl radical using the matrix isolation technique in combination with density functional theory (B3LYP/cc-pVTZ) computations. The hitherto unknown phenylselenyl peroxy radical was synthesized by co-condensation of the phenylselenyl radical with molecular ground state triplet oxygen from the gas phase and subsequent trapping in argon matrices at 10 K. The experimental IR spectra including ¹⁸O isotopically labelled materials compare well with the data obtained from B3LYP/cc-pVTZ computations. Upon 312 nm irradiation, the phenylselenyl peroxy radical isomerizes to the thermodynamically more stable equally novel phenylselenoyl radical.