The hypothiocyanite radical OSCN and its isomers

Zhuang Wu; Jian Xu; Qifan Liu; Xuelin Dong; Dingqing Li; Nicole Holzmann; Gernot Frenking; Tarek Trabelsi; Joseph S. Francisco; Xiaoqing Zeng

doi:10.1039/C7CP02774E

The hypothiocyanite radical OSCN and its isomers†

Zhuang Wu,^a Jian Xu,^a Qifan Liu,^a Xuelin Dong,^a Dingqing Li,^a Nicole Holzmann,^b Gernot Frenking,

*^cd Tarek Trabelsi,^e Joseph S. Francisco*^f and Xiaoqing Zeng

*^a

Author affiliations

* Corresponding authors

^a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China
E-mail: xqzeng@suda.edu.cn

^b STFC Rutherford Appleton Laboratory, Harwell Oxford, Didcot OX11 0QX, UK

^c Fachbereich Chemie, Philipps-Universität Marburg, Marburg D-35032, Germany
E-mail: frenking@chemie.uni-marburg.de

^d Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia-San Sebastian, Spain

^e Department of Chemistry, University of Nebraska – Lincoln, Lincoln, Nebraska 68526, USA
E-mail: francisc@purdue.edu

^f Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA

Abstract

A biologically relevant reactive sulfur species (RSS), the hypothiocyanite radical OSCN, is generated in the gas phase through flash vacuum pyrolysis (FVP) of trifluoromethyl sulfinyl cyanide CF₃S(O)CN at ca. 1000 K. Upon UV light irradiation (365 nm), OSCN rearranges to novel isomers OSNC and SOCN, and further visible light irradiation (400 ± 20 nm) leads to reverse isomerization. The identification of OSCN, OSNC, and SOCN in cryogenic matrices (Ar and N₂, 2.8 K) with IR spectroscopy is supported by quantum chemical calculations up to the CCSD(T)-F12/VTZ-F12 level. The potential energy surface for the interconversion of OSCN isomers and their bonding properties are computationally explored by using the CCSD(T)-F12/VTZ-F12 and EDA–NOCV methods, respectively.

Physical Chemistry Chemical Physics

The hypothiocyanite radical OSCN and its isomers†

Abstract

Supplementary files

Article information

Download Citation

Permissions

The hypothiocyanite radical OSCN and its isomers

Social activity

Search articles by author

Spotlight

Advertisements