Ar-Matrix Studies of the Photochemical Reaction between CS2 and ClF: Prereactive Complexes and Bond Isomerism of the Photoproducts

In this work, prereactive complexes, reaction products, and conformational preferences derived from the photochemical reaction between CS2 and ClF were analyzed following the codeposition of the reactants trapped in argon matrices at cryogenic temperatures. After codeposition of CS2 and ClF diluted in Ar, the formation of van der Waals complexes is observed. When the mixture is subsequently irradiated by means of broad-band UV-visible light (225 ≤ λ ≤ 800 nm), fluorothiocarbonylsulfenyl chloride (FC(S)SCl) and chlorothiocarbonylsulfenyl fluoride (ClC(S)SF) are produced. These species exist as two stable planar anti- and syn-conformers (anti- and syn- of the C=S double bond with respect to the S–Cl or S–F single bond, respectively). For both novel molecules, anti-FC(S)SCl and anti-ClC(S)SF are the lowest-energy computed rotamers. As expected due to the photochemical activity of these species, additional reaction products due to alternative or subsequent photochannels are formed during this process.