Silicon-substituted derivatives of trifluoro(trifluoromethyl)silane. Some chemistry of the silicon-iodine bond in a polyhalo system

Article abstract of DOI:10.1021/ic50148a007

The fluoroiodosilane CF₃SiF₂I has been utilized to generate a series of compounds of formula CF₃SiF₂X, where X = Br, Cl, F, and OSiF₂CF₃; all but X = F are new compounds. Conversion of Si-I bonds to Si-X is effected by antimony(III) halides or, for oxygen, mercury(II) oxide. Each of the halodifluoro(trifluoromethyl)silanes undergoes pyrolytic decomposition at 100° to generate SiF₃X and CF₂, although the thermal decomposition of CF₃SiF₂I is quite complex. Each of the CF₃SiF₂X species (other than CF₃SiF₃) reacts with water vapor to generate CF₃SiF₃ and, for X = Br or I, CF₂HX. The halodifluoromethanes evidently result from the reaction of CF₂ with HX - the CF₂ in turn resulting from the interaction of water vapor and CF₃SiF₃ at room temperature. Correlations of fluorine chemical shifts and directly bonded silicon-fluorine coupling constants between CF₃SiF₂X species and the corresponding SiF₃X species are presented.