The SF3+ cation has been thought to be the reactive species in the deoxofluorination reactions using SF4. In the present work, SF3+ salts of the SbF6- and AsF6- anions have been structurally characterized and their phase properties were studied. The reactions of the [SF3]+ cation with nitrogen bases namely pyridine, acetonitrile, 4-dimetyhlaminopyridine, and 1,10-phenanthroline were investigated at low temperature. It was found that the [SF3]+ cation combines with two molecules of pyridine and acetonitrile at low temperature to give [SF3(NC5H5)2]+ and [SF3(CH3CN)2]+ cationic Lewis acid base adducts. The reaction with 1,10-phenanthroline, yielded the [SF3(1,10-phenanthroline)]+ Lewis acid base adduct. The reaction of SF3+ with the strong Lewis base dimethylaminopyridine (DMAP), on the other hand, resulted in the formation of [SF2(DMAP)2]2+ and [SF(DMAP)4]3+ cations. Initial investigations on the use of SF3+ salts in CH3CN/C5H5N as fluorinating reagents showed facile conversion of carboxylic acids to acyl fluorides.

Properties and reactivity of SF<sub>3</sub><sup>+</sup> salts

248th National Meeting (2014)

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Properties and reactivity of SF3+ salts

Properties and reactivity of SF₃⁺ salts