Unusual nitrene reactivity: imine formation in the photochemical reaction of a borylnitrene with ethene.

ABSTRACT: The cycloaddition of nitrenes with olefins is an important method for the synthesis of aziridines. We report here that the reaction of catecholato borylnitrene CatBN with ethene upon long wavelength photoirradiation (λ > 550 nm) gives not only the expected aziridine, but also the imine CatBN[double bond, length as m-dash]CHCH₃ under cryogenic matrix isolation conditions in solid neon at 4 K. Computational analysis reveals that the photochemically generated singlet CatBN (¹A₁ electronic state) can react with ethene to form the aziridine and a singlet 1,3-diradical intermediate. The latter arises from multi-state reactivity involving the nearly degenerate ¹A₁ and ¹A₂ nitrene singlet states. The singlet 1,3-di

SUBMITTER: Bhagat V 

PROVIDER: S-EPMC12728564 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature