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Updated: May 10, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Synthesis of [N(CH3)4]2O3SOSO2(s) and [N(CH3)4]2[(O2SO)2SO2]·SO2(s) containing (SO4)(SO2)x(2-) x = 1, 2, members of a
Pablo Bruna1, Andreas Decken, Friedrich Grein
1Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada.
Abstract:
One mole equivalent of SO2 reversibly reacts with [N(CH3)4]2SO4(s) to give [N(CH3)4]2S2O6(s) (1) containing the [O3SOSO2](2-), shown by Raman and IR to be an isomer of the [O3SSO3](2-) dianion. The experimental and calculated (B3PW91/6-311+G(3df)) vibrational spectra are in excellent agreement, and the IR spectrum is similar to that of the isoelectronic O3ClOClO2. Crystals of [N(CH3)4]2(O2SO)2SO2·SO2 (2) were isolated from solutions of [N(CH3)4]2SO4 in liquid SO2. The X-ray structure showed that 2 contained the [(O2SO)2SO2](2-) dianion. The characterized N(CH3)4(+) salts 1 and 2 are the first two members of the (SO4)(SO2)x(2-) class of sulfur oxydianions analogous to the well-known small cation salts of the SO4(SO3)x(2-) polysulfates.
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