Structure and Chemistry of Sulfur Tetrafluoride James
STRUCTURE AND CHEMISTRY OF SULFUR TETRAFLUORIDE JAMES T. GOETTEL B.Sc., University of Alberta, 2011 A Thesis Submitted to the School of Graduate Studies of the University of Lethbridge in Partial Fulfilment of the Requirements for the Degree MASTER OF SCIENCE Department of Chemistry and Biochemistry University of Lethbridge LETHBRIDGE, ALBERTA, CANADA © James T. Goettel, 2013 ABSTRACT Sulfur tetrafluoride was shown to be a useful reagent in preparing salts of VII − V − VII − Re O2F4 , I OF4 , and I O2F4 . Sulfur tetrafluoride reacts with oxo-anions in acetonitrile or anhydrous HF (aHF) via fluoride-oxide exchange reactions to quantitatively form oxide fluoride salts, as observed by Raman and 19F NMR spectroscopy. Pure Ag[ReO2F4] as well as the new CH3CN coordination compounds [Ag(CH3CN)2][ReO2F4] and [Ag(CH3CN)4][ReO2F4]•CH3CN were prepared. The latter was characterized by single-crystal X-ray diffraction. The reaction of [N(CH3)4]IO3 with SF4 in acetonitrile gave the new [N(CH3)4][IOF4] salt. Sulfur tetrafluoride forms Lewis acid-base adducts with pyridine and its derivatives, i.e., 2,6-dimethylpyridine, 4-methylpyridine and 4- dimethylaminopyridine, which have recently been identified in our lab. In the presence of HF, the nitrogen base in the SF4 base reaction systems is protonated, which can formally be viewed as solvolysis of the SF4•base adducts by HF. The resulting salts have been studied by Raman spectroscopy and X-ray crystallography. + − Crystal structures were obtained for pyridinium salts: [HNC5H5 ]F •SF4, + − − + − [HNC5H5 ]F [HF2 ]•2SF4; 4-methylpyridinium salt: [HNC5H4(CH3) ]F •SF4, + − [HNC5H4(CH3) ][HF2 ]; 2,6-dimethylpyridinium salt: + − − [HNC5H3(CH3)2 ]2[SF5 ]F •SF4; 4-dimethylaminopyridinium salts: + − − + − [HNC5H4N(CH3)2 ]2[SF5 ]F •CH2Cl2, [NC5H4N(CH3)2 ][HF2 ]•2SF4; and the 4,4’- + − 2+ − bipyridinium salts: [HNH4C5−C5H4N ]F •2SF4, [HNH4C5−C5H4NH ]2F •4SF4.
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