Chloro- and Dichloro-methylsulfonyl Nitrenes: Spectroscopic Characterization, Photoisomerization, and Thermal Decomposition.

ABSTRACT: Chloro- and dichloro-methylsulfonyl nitrenes, CH₂ClS(O)₂N and CHCl₂S(O)₂N, have been generated from UV laser photolysis (193 and 266 nm) of the corresponding sulfonyl azides CH₂ClS(O)₂N₃ and CHCl₂S(O)₂N₃, respectively. Both nitrenes have been characterized with matrix-isolation IR and EPR spectroscopy in solid N₂ (10 K) and glassy toluene (5 K) matrices. Triplet ground-state multiplicity of CH₂ClS(O)₂N (|D/hc| = 1.57 cm-1 and |E/hc| = 0.0026 cm-1) and CHCl₂S(O)₂N (|D/hc| = 1.56 cm-1 and |E/hc| = 0.0042 cm-1) has been confirmed. In addition, dichloromethylnitrene CHCl₂N (|D/hc| = 1.57 cm-1 and |E/hc| = 0 cm-1), formed from SO₂-elimination in CHCl₂S(O)₂N, has also been identified for the first time. Upon UV light irradiation (365 nm), the two sulfonyl nitrenes R⁻S(O)₂N (R = CH₂Cl and CHCl₂)

SUBMITTER: Yang Y 

PROVIDER: S-EPMC6321523 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature