Abstract: | The Sulfenic Fluorides CF3SF and CF2CISF and their Dimers The reactions of RfSCl (Rf = CF3, CF2Cl) with HgF2 and AgF give RfSF and the dimer product RfSF2SRf in high yield and various ratios, in contrast, activated KF leads only to RfSF in low yield. A complex of transition metal and sulfenic halide as an intermediate step is discussed for the dimerisation. As liquid CF3SF2SCF3 disproportionates into CF3SF3 and CF3SSCF3 and the hydrolysis of CF3SF2SCF3 gives the stable compound CF3S(O)SCF3 · PF3 reacts with RfSF as well as with RfSF2SRf to RfSPF4. The products of the spontaneous decomposition of CF2ClSF were investigated. I.r., n.m.r., and mass spectra are reported and discussed. It was possible to carry out vapour pressure measurements of CF2ClSF. |