Parent Thioketene S-Oxide H2 CCSO: Gas-Phase Generation, Structure, and Bonding Analysis

Zhuang Wu; Jian Xu; Liubov Sokolenko; Yurii L Yagupolskii; Ruijuan Feng; Qian Liu; Yan Lu; Lili Zhao; Israel Fernández; Gernot Frenking; Tarek Trabelsi; Joseph S Francisco; Xiaoqing Zeng

doi:10.1002/chem.201703161

Parent Thioketene S-Oxide H₂ CCSO: Gas-Phase Generation, Structure, and Bonding Analysis

Chemistry. 2017 Nov 21;23(65):16566-16573. doi: 10.1002/chem.201703161. Epub 2017 Oct 30.

Authors

Zhuang Wu¹, Jian Xu¹, Liubov Sokolenko², Yurii L Yagupolskii², Ruijuan Feng¹, Qian Liu¹, Yan Lu¹, Lili Zhao³, Israel Fernández⁴, Gernot Frenking^{3

5

6}, Tarek Trabelsi⁷, Joseph S Francisco⁸, Xiaoqing Zeng¹

Affiliations

¹ College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
² Organofluorine Chemistry Department, Institute of Organic Chemistry, National Academy of Sciences of (Ukraine), Murmanskaya str. 5, 02660, Kiev-94, Ukraine.
³ Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 211816, China.
⁴ Departamento de Química Orgánica I and Centro de Innovación en Química Avanzada, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040, Madrid, Spain.
⁵ Fachbereich Chemie, Philipps-Universität Marburg, Marburg, 35032, Germany.
⁶ Donostia International Physics Center (DIPC), P.K. 1072, 20080, Donostia-San Sebastian, Spain.
⁷ University of Nebraska-Lincoln, Lincoln, Nebraska, 68526, USA.
⁸ Department of Chemistry, Purdue University, West Lafayette, Indiana, 47907, USA.

PMID: 28872716
DOI: 10.1002/chem.201703161

Abstract

The parent thioketene S-oxide H₂ CCSO has been generated in the gas phase through flash vacuum pyrolysis (ca. 1000 K) of vinyl sulfoxide H₂ CC(Br)-S(O)CF₃ via the intermediacy of a novel vinyl sulfinyl radical H₂ C=C(Br)-SO (syn and anti conformers). Upon irradiation at 266 nm, H₂ CCSO decomposes into HCCH/SO and H₂ CS/CO in cryogenic Ar matrix. Whereas, visible-light irradiations result in syn↔anti conformational interconversion in H₂ C=C(Br)-SO. The molecular structures of H₂ CCSO and isomers are computationally studied at the CCSD(T)-F12/VTZ-F12 level of theory, and the bonding properties of H₂ CCSO are analyzed with the EDA-NOCV method at the M06-2X/TZ2P level.

Keywords: bonding analysis; density functional calculations; flash vacuum pyrolysis; radicals; sulfines.