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Parent Thioketene S‐Oxide H 2 CCSO: Gas‐Phase Generation, Structure, and Bonding Analysis
Author(s) -
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
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703161
Subject(s) - flash vacuum pyrolysis , conformational isomerism , sulfoxide , gas phase , chemistry , oxide , pyrolysis , crystallography , photochemistry , molecule , organic chemistry
The parent thioketene S ‐oxide H 2 CCSO has been generated in the gas phase through flash vacuum pyrolysis (ca. 1000 K) of vinyl sulfoxide H 2 CC(Br)−S(O)CF 3 via the intermediacy of a novel vinyl sulfinyl radical H 2 C=C(Br)−SO ( syn and anti conformers). Upon irradiation at 266 nm, H 2 CCSO decomposes into HCCH/SO and H 2 CS/CO in cryogenic Ar matrix. Whereas, visible‐light irradiations result in syn ↔ anti conformational interconversion in H 2 C=C(Br)−SO. The molecular structures of H 2 CCSO and isomers are computationally studied at the CCSD(T)‐F12/VTZ‐F12 level of theory, and the bonding properties of H 2 CCSO are analyzed with the EDA‐NOCV method at the M06‐2X/TZ2P level.