Preparation of FC(S)SF, FC(S)SeF and FC(Se)SeF through matrix photochemical reactions of F2with CS2, SCSe, and CSe2

BAVA, YANINA B.; COZZARÍN, MELINA V.; DELLA VÉDOVA, CARLOS O.; WILLNER, HELGE; ROMANO, ROSANA M.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS

ROYAL SOC CHEMISTRY

Año: 2021 vol. 23 p. 20892 - 20900

1463-9076

The reactions of F2 with CS2, SCSe, and CSe2, respectively, were analyzed under matrix conditions by co-deposition of the halogen with the triatomic molecules trapped in argon matrices at cryogenic temperatures. In all cases, after co-deposition, the formation of the respective van der Waals complexes is observed. When each mixture is subsequently irradiated by means of broad-band UV-visible light (200 ≤ λ ≤ 800 nm), FC(S)SF, fluorothiocarbonylsulfenyl fluoride, FC(S)SeF, fluorothiocarbonylselenyl fluoride and FC(Se)SeF, fluoroselenocarbonylselenyl fluoride are produced, respectively. All these species exist as two stable planar syn- and anti-conformers (syn- and anti- of the C=Z double bond, Y = S, Se, with respect to the S-F or Se-F single bond, respectively). For FC(S)SF, syn- is the rotamer with the lowest energy, while for both FC(S)SeF and FC(Se)SeF the anti-form is the lowest energy conformer. In all cases, other products due to alternative or subsequent photochannels are observed during the photochemical processes carried out in argon matrices at cryogenic temperatures.