Article pubs.acs.org/JPCA
Mechanistic Insight into Decomposition of 2H‑Azirines: Electronic Structure Calculations and Dynamics Simulations Ye Liu,† Peijie Guan,† Yating Wang,† Lihong Liu,*,† and Jun Cao*,†,‡ †
Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China ‡ Guizhou Provincial Key Laboratory of Computational Nano-material Science, Guizhou Normal College, Guiyang, Guizhou 550018, China S Supporting Information *
ABSTRACT: In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore the decomposition reactions of 2Hazirine, 2-phenyl-2H-azirine, and 3-phenyl-2H-azirine in gas phase. Thermal cleavage of the C−C single bond yields nitrile ylides as products with a high barrier (>50.0 kcal mol−1). On the other hand, photochemical cleavage reactions starting from the 1nπ* state of 2H-azirine and 3-phenyl-2H-azirine are ultrafast nonadiabatic processes (
