The first quaternary salts of pyridine (2), N-methyl imidazole (3), N-propyl triazole (4), and pyridazine (5) that contain the pentafluorosulfanyl (SF5) group were prepared and characterized. Neat reactions of the aromatic nitrogen compounds with SF5(CF2)(n)(CH2)(m)\ (n = 2 or 4, m = 2 or 4) gave quaternary iodides 6a-c, 7a-c, 8a, and 9a,b, which were metathesized with LiN(SO2CF3)(2) to form the bis(trifluoromethylsulfonyl)am ides 10a-c, 11a-c, 12a, and 13a,b, in high yields. With the exception of the pyridine bis(trifluoromethylsulfonyl)amide salts, the compounds melted or exhibited a T-g at <0 degreesC. The methylimidazolium, pyridinium, and pyridazinium salts exhibited densities of similar to2 g/cm(3). Particularly striking was the density of CF3(CF2)(5)(CH2)(2)-pyridazinium N(CF3SO2)(2) measured at 2.13 g/cm(3); however, an atypically high density for the 1-CF3(CF2)(5)(CH2)(2)-3-methyl imidazolium amide (14) was also observed at 1.77 g/cm(3). All quaternary salts were characterized via IR, F-19, H-1, and C-13 NMR spectra and elemental analyses.