Parent Thioketene S-Oxide H2CCSO: Gas-Phase Generation,Structure, and Bonding Analysis
Zhuang Wu[a], Jian Xu[a], Liubov Sokolenko[b], Yurii L. Yagupolskii[b], Ruijuan Feng[a],Qian Liu[a], Yan Lu[a], Lili Zhao*[c], Israel Fern#ndez[d], Gernot Frenking*[c, e], Tarek Trabelsi[f],Joseph S. Francisco*[g], and Xiaoqing Zeng*[a]（曾小庆）
[a]College of Chemistry, Chemical Engineering and Materials Science
Soochow University, Suzhou 215123 (China)
[b]Organofluorine Chemistry Department, Institute of Organic Chemistry
National Academy of Sciences of (Ukraine) Murmanskaya str. 5, 02660 Kiev-94 (Ukraine)
[c]Institute of Advanced Synthesis School of Chemistry and Molecular Engineering Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816 (China)
[d]Departamento de Qu&mica Org#nica I and Centro de Innovacijn en
Qu&mica Avanzada, Facultad de Ciencias Qu&micas Universidad Complutense de Madrid, 28040 Madrid (Spain)
[e]Fachbereich Chemie, Philipps-Universit-t Marburg Marburg 35032 (Germany) and Donostia International Physics Center (DIPC) P.K. 1072, 20080 Donostia-San Sebastian (Spain)
[f]University of Nebraska—Lincoln Lincoln, Nebraska 68526 (USA)
[g]Department of Chemistry, Purdue University West Lafayette, Indiana 47907 (USA)
Chem . Eur . J .2017，23:16566--16573
The parent thioketene S-oxide H2CCSO has been generated in the gas phase through flash vacuum pyrolysis (ca. 1000 K) of vinyl sulfoxide H2CC(Br)−S(O)CF3 via the intermediacy of a novel vinyl sulfinyl radical H2C=C(Br)−SO (syn and anti conformers). Upon irradiation at 266 nm, H2CCSO decomposes into HCCH/SO and H2CS/CO in cryogenic Ar matrix. Whereas, visible-light irradiations result in syn↔anti conformational interconversion in H2C=C(Br)−SO. The molecular structures of H2CCSO and isomers are computationally studied at the CCSD(T)-F12/VTZ-F12 level of theory, and the bonding properties of H2CCSO are analyzed with the EDA-NOCV method at the M06-2X/TZ2P level.
链接：http://onlinelibrary.wiley.com/doi/10.1002/chem.201703161/abstract;jsessionid=D0ADEC6B613049E4AC460407D1AC7747.f03t03