TY - JOUR
T1 - Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO
AU - Wu, Zhuang
AU - Feng, Ruijuan
AU - Xu, Jian
AU - Lu, Yan
AU - Lu, Bo
AU - Yang, Tao
AU - Frenking, Gernot
AU - Trabelsi, Tarek
AU - Francisco, Joseph S.
AU - Zeng, Xiaoqing
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/1/31
Y1 - 2018/1/31
N2 - 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 CF3S(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.
AB - 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 CF3S(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.
UR - http://www.scopus.com/inward/record.url?scp=85041453988&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b12622
DO - 10.1021/jacs.7b12622
M3 - 文章
C2 - 29307182
AN - SCOPUS:85041453988
SN - 0002-7863
VL - 140
SP - 1231
EP - 1234
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -