Photoisomerization of matrix-isolated bis(trifluoromethyl) sulfoxide: formation of the sulfenic ester CF3SOCF3

S E Ulic; S von Ahsen; H Willner

doi:10.1021/ic049800r

Photoisomerization of matrix-isolated bis(trifluoromethyl) sulfoxide: formation of the sulfenic ester CF3SOCF3

Inorg Chem. 2004 Aug 23;43(17):5268-74. doi: 10.1021/ic049800r.

Authors

S E Ulic¹, S von Ahsen, H Willner

Affiliation

¹ CEQUINOR, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, 1900 La Plata, Republic of Argentina. sonia@quimica.unlp.edu.ar

PMID: 15310204
DOI: 10.1021/ic049800r

Abstract

Bis(trifluoromethyl) sulfoxide, CF(3)S(O)CF(3), isolated in noble gas matrixes at low temperatures, isomerizes upon UV irradiation into the sulfenic ester CF(3)SOCF(3). The new species is characterized spectroscopically, and the vibrational assignment is supported by (18)O isotopic labeling experiments and by DFT calculations. The calculated structural parameters of CF(3)SOCF(3) are compared with the calculated and experimental data of the related compounds CF(3)SSCF(3) and CF(3)OOCF(3). In addition, the computed enthalpy differences between the sulfoxide R(2)S=O and sulfenate RSOR structures for R = H, F, CH(3), and CF(3) are included.