曾小庆教授与德国马尔堡大学Gernot Frenking教授、 美国内布拉斯加大学Joseph S. Francisco教授合作在 J. Am. Chem. Soc. 上发表研究论文

Photoinduced Sulfur–Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO

Zhuang Wu,Ruijuan Feng,Jian Xu,Yan Lu,Bo Lu,Tao Yang,Gernot Frenking*,Tarek Trabelsi§,Joseph S. Francisco*§, andXiaoqing 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