Caged Nitric Oxide-Thiyl Radical Pairs

Zhuang Wu; Changyun Chen; Jie Liu; Yan Lu; Jian Xu; Xiangyang Liu; Ganglong Cui; Tarek Trabelsi; Joseph S Francisco; Artur Mardyukov; André K Eckhardt; Peter R Schreiner; Xiaoqing Zeng

doi:10.1021/jacs.8b12746

Caged Nitric Oxide-Thiyl Radical Pairs

J Am Chem Soc. 2019 Feb 27;141(8):3361-3365. doi: 10.1021/jacs.8b12746. Epub 2019 Feb 18.

Authors

Affiliations

¹ College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , China.
² Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry , Beijing Normal University , Beijing 100875 , China.
³ Department of Earth and Environmental Science and Department of Chemistry , University of Pennsylvania , Philadelphia , Pennsylvania 19104 , United States.
⁴ Institute of Organic Chemistry , Justus Liebig University , Heinrich-Buff-Ring 17 , 35392 Giessen , Germany.

PMID: 30758958
DOI: 10.1021/jacs.8b12746

Abstract

S-Nitrosothiols (RSNO) are exogenous and endogenous sources of nitric oxide in biological systems due to facile homolytic cleavage of the S-N bonds. By following the photolytic decomposition of prototypical RSNO (R = Me and Et) in Ne, Ar, and N₂ matrixes (<10 K), elusive caged radical pairs consisting of nitric oxide (NO•) and thiyl radicals (RS•), bridged by O···S and H···N connections, were identified with IR and UV/vis spectroscopy. Upon red-light irradiation, both caged radical pairs (RS•···•ON) vanish and reform RSNO. According to the calculation at the CASPT2(10,8)/cc-pVDZ level (298.15 K), the dissociation energy of MeS•···•ON amounts to 4.7 kcal mol^-1.

Publication types

Research Support, Non-U.S. Gov't