title: 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 new class of sulfur oxydianions.
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.
authors.affiliation: Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada.
authors.forename: Pablo
authors.initials: P
authors.lastname: Bruna
authors.forename: Andreas
authors.initials: A
authors.lastname: Decken
authors.forename: Friedrich
authors.initials: F
authors.lastname: Grein
authors.forename: Jack
authors.initials: J
authors.lastname: Passmore
authors.forename: J Mikko
authors.initials: JM
authors.lastname: Rautiainen
authors.forename: Stephanie
authors.initials: S
authors.lastname: Richardson
authors.forename: Tom
authors.initials: T
authors.lastname: Whidden