Zhuang Wu† Ruijuan Feng† Jian Xu† Yan Lu† Bo Lu† Tao Yang‡ Gernot Frenking*‡∥Tarek Trabelsi§ Joseph S. Francisco*§ Xiaoqing Zeng*†(曾小庆)
†College of Chemistry, Chemical Engineering and Materials Science,Soochow University, 215123 Suzhou,China
‡Fachbereich Chemie,Philipps-Universität Marburg, Marburg D-35032,Germany
∥Institute of Advanced Synthesis,Nanjing Tech University, 211816 Nanjing,China
§Department of Chemistry,University of Nebraska−Lincoln, Lincoln, Nebraska 68588,United States
J. Am. Chem. Soc.,2018,140(4), 1231--1234
An exotic ternary S, N, O heterocumulene OSNSO insyn-syn(A) andsyn-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), bothAandB, isolated in cryogenic matrices (N2, Ne, Ar, and Kr, <30 K), convert to a higher-energyanti-anticonformer (C). The reverse conformational transformation occurs either through S═N bond rotation (CtoAandB) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (CtoA) in the temperature range of 20–30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol–1has been experimentally determined.
链接:https://pubs.acs.org/doi/10.1021/jacs.7b12622