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JOURNAL ARTICLE
RESEARCH SUPPORT, NON-U.S. GOV'T
Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO.
Journal of the American Chemical Society 2018 January 32
An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated in the gas phase through flash vacuum pyrolysis of CF3 S(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A and B, isolated in cryogenic matrices (N2 , Ne, Ar, and Kr, <30 K), convert to a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either through S═N bond rotation (C to A and B) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (C to A) in the temperature range of 20-30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol-1 has been experimentally determined.
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