Photochemistry of 1-Phenyl-1-diazopropane and Its Diazirine Isomer: A CASSCF and MS-CASPT2 Study.

ABSTRACT: In this work, we studied the wavelength (520 or 350 nm) dependence of the photochemical decomposition of 1-phenyl-1-diazopropane (PDP) and 1-phenyl-1-propyl diazirine (PED) by means of high-level ab initio quantum chemical calculations (CASSCF and MS-CASPT2) to obtain qualitative and quantitative results. It is found that the photochemistry of PDP is governed by nonradiative deactivation processes that can involve one or two S₁/S₀ conical intersections (CI1 and CI2) depending on the wavelength of the radiation; CI2 is only accessible at the shortest wavelength. It is demonstrated that the main intermediate of the photochemistry of the titled compounds is 1-ethyl-1-phenyl carbene (EPC). Upon irradiation of PDP<

SUBMITTER: Soto J 

PROVIDER: S-EPMC9677432 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature