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SELECTED REACTIONS OF FLUORINE-FLUOROSULFATE, FOSO2F

TitleSELECTED REACTIONS OF FLUORINE-FLUOROSULFATE, FOSO2F
Publication TypeJournal Article
Year of Publication1992
AuthorsWillner, H, Mistry, F, Aubke, F
JournalJournal of Fluorine Chemistry
Volume59
Pagination333-349
Date PublishedDec
Type of ArticleArticle
ISBN Number0022-1139
KeywordsDERIVATIVES, GOLD(III) FLUOROSULFATE, halogen, ION, SPECTRA, TRIS(FLUOROSULFATE)
Abstract

The reactions of fluorine-fluorosulfate, FOSO2F, with SSF2, SeF4, AsF3 and MoF5 have been studied, and its previously reported reactions with SF4, Br2 and I2 re-investigated in order to test its suitability as a synthetic reagent. All substrates reacted exothermically, and sometimes explosively, between 80-298 K. The presence of the byproducts obtained may be rationalized by the thermal decomposition of some of the FOSO2F, which proceeds along two pathways, i.e. FOSO2F –> 1/2O2 + SO2F2 and FOSO2F –> 1/2F2 + 1/2S2O6F2, during the extremely exothermic reactions via radical intermediates. The fluorine formed gives rise to fully fluorinated products, and the SO3F. radicals, initially formed, either dimerize to give S2O6F2 or decompose to O2 and S2O5F2. Element fluoride-fluorosulfates, when formed at all, were obtained in low yields only when SO2F2 or SO2FCl were used as suitable moderators. The complete vibrational spectra of EF5OSO2F (E = S, Se or Te) have been studied and assigned. The reactions of I2, Br2 and AsF3 with FOSO2F yielded viscous liquids of the approximate, non-stoichiometric composition EFn(SO5F)5-n (E = As or I) and EFn(SO3F)3-n (E = Br), with n = non-integral number. All compounds were characterized by their vibrational and F-19 NMR spectra, and in the case of SeF5OSO2F by Se-77 NMR methods.

URL<Go to ISI>://A1992KF32100004