Science of Synthesis

Argyropoulos, N. G., Science of Synthesis, (2004) 13, 80.

The dithionitronium cation [NS2]+, the sulfur analogue of the nitronium cation [NO2]+, is a useful building block for the synthesis of 1,3,2-dithiazolium salts. The dithionitronium cation may be considered as a pseudo 1,3-dipole, with two mutually perpendicular three-center, four-electron arrays, closely related to that of typical 1,3-dipoles. This cation, in the form of its hexafluoroarsenate salt ‌41‌, reacts quantitatively with alkynes to give 1,3,2-dithiazolium salts ‌42‌ (‌Scheme 12‌).[‌23‌–‌28‌] A concerted inverse-electron demand process seems to operate in the cycloaddition,[‌27‌] which is performed by mixing equimolar amounts of the reactants in liquid sulfur dioxide, then allowing the solution to warm to room temperature. Dithionitronium hexafluoroarsenate (‌41‌)[‌43‌] may be obtained, in liquid sulfur dioxide solution, in two ways; either from octasulfur di(hexafluoroarsenate) [S8(AsF6)2],[‌44‌] sodium azide, and arsenic pentafluoride, or from sulfur, tetrasulfur tetranitride (‌40‌),[‌45‌] and arsenic pentafluoride. A procedure giving highly pure dithionitronium hexafluoroarsenate has been described[‌46‌]. Both routes to the hexafluoroarsenate ‌41‌ require specially designed apparatus.[‌24‌,‌26‌,‌46‌]

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‌Meeeeeeeeee 88‌

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Meeeeeeeeeee Meeeeeeee

8-Meeeee-8,8,8-eeeeeeeeeeee Meeeeeeeeeeeeeeeee (‌88‌, M8 = M; M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

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Meeeeee (8.88 e, 8.8 eeee) eee eeeeeeeee eeee eeeeeeeeeeeeeee eeeeeeeeeeeeeeeeee ‌88‌ (8.88 e, 8.8 eeee),[‌88‌] eeeeeeee eeee M8, M8M8, eee MeM8, ee eee MM8 (8.8 e). M eeeee-eeeeee eeee eee eeeeee ee eeeeeee ee ee, eeeee eeeeeeeee eeeeeee eeeee eeeee ee eeeeeeee, eee eeee ee eeeeee eeeee. Meeee 8 e, MM8MeM (8.88 e) eee eeeee, eeeeee e eeeee eeee eeeee eeeeee eeeee eeeee e eeeee eeeee eeeee. Mee eee eeeeee eeee eeeeeeeee eeee eee eee eeeee, eee eee eeeeeee eee eeeeeee eeeeee ee eeeeeeeee eeeee eeeee (8.88 e) ee eee eeee eee eeeee eeeeee-eeee eeeeeeee (8.88 e) ee eee eeeee. Meee eeeeeeee eeee eeeeeeeee (ee MM); eeeee eeeee: 8.88 e (88.8%); ee 888°M (eee, eeeeee eeee).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8e, 88.