母体硫代乙烯亚砜H CCSO：气相生成、结构及键合分析
Parent Thioketene S-Oxide H CCSO: Gas-Phase Generation, Structure, and Bonding Analysis.
作者信息
Wu Zhuang, Xu Jian, Sokolenko Liubov, Yagupolskii Yurii L, Feng Ruijuan, Liu Qian, Lu Yan, Zhao Lili, Fernández Israel, Frenking Gernot, Trabelsi Tarek, Francisco Joseph S, Zeng Xiaoqing
机构信息
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Organofluorine Chemistry Department, Institute of Organic Chemistry, National Academy of Sciences of (Ukraine), Murmanskaya str. 5, 02660, Kiev-94, Ukraine.
出版信息
Chemistry. 2017 Nov 21;23(65):16566-16573. doi: 10.1002/chem.201703161. Epub 2017 Oct 30.
The parent thioketene S-oxide H CCSO has been generated in the gas phase through flash vacuum pyrolysis (ca. 1000 K) of vinyl sulfoxide H CC(Br)-S(O)CF via the intermediacy of a novel vinyl sulfinyl radical H C=C(Br)-SO (syn and anti conformers). Upon irradiation at 266 nm, H CCSO decomposes into HCCH/SO and H CS/CO in cryogenic Ar matrix. Whereas, visible-light irradiations result in syn↔anti conformational interconversion in H C=C(Br)-SO. The molecular structures of H CCSO and isomers are computationally studied at the CCSD(T)-F12/VTZ-F12 level of theory, and the bonding properties of H CCSO are analyzed with the EDA-NOCV method at the M06-2X/TZ2P level.
母体硫代乙烯亚砜H CCSO已通过对乙烯基亚砜H CC(Br)-S(O)CF进行闪蒸真空热解（约1000 K），经由新型乙烯基亚磺酰基自由基H C=C(Br)-SO（顺式和反式构象体）在气相中生成。在266 nm波长下照射时，H CCSO在低温氩气基质中分解为HCCH/SO和H CS/CO。然而，可见光照射会导致H C=C(Br)-SO中顺式↔反式构象互变。在CCSD(T)-F12/VTZ-F12理论水平上对H CCSO及其异构体的分子结构进行了计算研究，并在M06-2X/TZ2P水平上用EDA-NOCV方法分析了H CCSO的键合性质。
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