Journal article

Publication year: 2019

Pages: 3361-3365

Journal: Journal of the American Chemical Society

Volume number: 141

Issue number: 8

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/jacs.8b12746

Publisher: American Chemical Society

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 N-2 matrixes (<10 K), elusive caged radical pairs consisting of nitric oxide (NO center dot) and thiyl radicals (RS center dot), bridged by O center dot center dot center dot S and H center dot center dot center dot N connections, were identified with IR and UV/vis spectroscopy. Upon red-light irradiation, both caged radical pairs (RS center dot center dot center dot 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 center dot center dot center dot ON amounts to 4.7 kcal mol(-1).

Harvard Citation style: Wu, Z., Chen, C., Liu, J., Lu, Y., Xu, J., Liu, X., et al. (2019) Caged Nitric Oxide-Thiyl Radical Pairs, Journal of the American Chemical Society, 141(8), pp. 3361-3365. https://doi.org/10.1021/jacs.8b12746

APA Citation style: Wu, Z., Chen, C., Liu, J., Lu, Y., Xu, J., Liu, X., Cui, G., Trabelsi, T., Francisco, J., Mardyukov, A., Eckhardt, A., Schreiner, P., & Zeng, X. (2019). Caged Nitric Oxide-Thiyl Radical Pairs. Journal of the American Chemical Society. 141(8), 3361-3365. https://doi.org/10.1021/jacs.8b12746