三氟甲基亚磺酰基和氧硫基自由基。

The Trifluoromethyl Sulfinyl and Oxathiyl Radicals.

作者信息

Wu Zhuang, Xu Jian, Deng Guohai, Chu Xianxu, Sokolenko Liubov, Trabelsi Tarek, Francisco Joseph S, Eckhardt André K, Schreiner Peter R, Zeng Xiaoqing

机构信息

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P.R. China.

Organofluorine Chemistry Department, Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev-94, 02660, Ukraine.

出版信息

Chemistry. 2018 Feb 1;24(7):1505-1508. doi: 10.1002/chem.201705142. Epub 2017 Nov 16.

DOI:10.1002/chem.201705142

PMID:29083511

Abstract

Two hitherto unreported sulfur-centered radicals CF SO and CF OS were generated in the gas phase through high-vacuum flash pyrolyses of sulfoxide CF S(O)X (X=CF , Cl, PhO) precursors. The CF OS molecule is the first experimental example that constitutes an oxathiyl radical. It was isolated and characterized by combining matrix-isolation IR and UV/Vis spectroscopy with quantum chemical computations up to the UCCSD(T)-F12/cc-pVTZ-F12 level of theory. Upon UV light irradiation (254 or 266 nm), sulfinyl radical (CF SO ) isomerizes to oxathiyl radical (CF OS ) in cryogenic noble gas matrices (Ar and Ne). Natural population analyses at the BP86/def2-TZVPP//UCCSD(T)-F12/cc-pVTZ-F12 level suggest that the spin density in CF OS is mainly localized on the sulfur atom (0.86), whereas, in CF SO the spin density is almost equally distributed on the sulfur (0.55) and oxygen (0.43) atoms.

摘要

通过亚砜CF S(O)X（X = CF 、Cl、PhO）前体的高真空快速热解，在气相中产生了两个迄今未报道的以硫为中心的自由基CF SO和CF OS。CF OS分子是构成氧硫基自由基的第一个实验实例。通过将基质隔离红外光谱和紫外/可见光谱与高达UCCSD(T)-F12/cc-pVTZ-F12理论水平的量子化学计算相结合，对其进行了分离和表征。在低温惰性气体基质（Ar和Ne）中，经紫外光照射（254或266 nm），亚磺酰基自由基（CF SO ）异构化为氧硫基自由基（CF OS ）。在BP86/def2-TZVPP//UCCSD(T)-F12/cc-pVTZ-F12水平上进行的自然布居分析表明，CF OS中的自旋密度主要定域在硫原子上（0.86），而在CF SO中，自旋密度几乎均匀分布在硫（0.55）和氧（0.43）原子上。