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Synthesis of (TDAE)(O2SSO2)(s) and discovery of (TDAE)(O2SSSSO2)(s) containing the first polythionite, [O2SSSSO2]2–
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Bruna, P. (Pablo), Decken, Andreas, Greer, S. (Scott), Grein, Friedrich, Jenkins, H. Donald Brooke, Mueller, Birgit, Passmore, Jack, Paulose, Tressia A. P., Rautiainen, J. Mikko, Richardson, Stephanie and Schriver, Melbourne J. (2013) Synthesis of (TDAE)(O2SSO2)(s) and discovery of (TDAE)(O2SSSSO2)(s) containing the first polythionite, [O2SSSSO2]2–. Inorganic Chemistry, Volume 52 (Number 23). pp. 13651-13662. doi:10.1021/ic4022195 ISSN 0020-1669.
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Official URL: http://dx.doi.org/10.1021/ic4022195
Abstract
Gaseous SO2 reacts with tetrakis(dimethylamino)ethylene (TDAE) in acetonitrile in a 2:1 stoichiometric ratio to give analytically pure insoluble purple (TDAE)(O2SSO2) (1) in about 80% yield. Crystals of (TDAE)(O2SSSSO2) (2) were obtained from orange solution over the purple solid. The Raman spectrum of [TDAE]2+ was established using (TDAE)(A) salts [A = 2Br–, 2Br–·2H2O (X-ray), 2[Br3]− (X-ray)]. Vibrational spectroscopy showed that [O2SSO2]2– in 1 has C2h geometry. The X-ray structure of 2 showed that it contained [O2SSSSO2]2–, the first example of a new class of sulfur oxyanions, the polythionites. The geometry of [O2SSSSO2]2– consists of S2 with an S–S bond length of 2.003(1) Å connected to two terminal SO2 moieties by much longer S–S bonds of 2.337(1) Å. Calculations (B3PW91/6-311+G(3df)) show that the structural units in [O2SSSSO2]2– are joined by the interaction of electrons in two mutually perpendicular π* SOMOs of the triplet-state diradical S2 with unpaired electrons in the π*-antibonding orbitals of the two terminal [SO2]•– and polarized to delocalize the negative charge equally onto the three fragments. Thermodynamic estimates show 2 to be stable with respect to loss of sulfur and formation of 1, in contrast to [O2SSSSO2]2– salts of small cations that are unstable toward the related dissociation. Reaction of TDAE with an excess of liquid SO2 led to (TDAE)(O3SOSO3)·SO2 (preliminary X-ray, Raman), (TDAE)(O3SSSSO3)·2SO2 (preliminary X-ray, Raman), and (TDAE)(O3SSO2) (Raman).
| Item Type: | Journal Article | ||||
|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Sodium salts, Vibrational spectra | ||||
| Journal or Publication Title: | Inorganic Chemistry | ||||
| Publisher: | American Chemical Society | ||||
| ISSN: | 0020-1669 | ||||
| Official Date: | 2013 | ||||
| Dates: |
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| Volume: | Volume 52 | ||||
| Number: | Number 23 | ||||
| Page Range: | pp. 13651-13662 | ||||
| DOI: | 10.1021/ic4022195 | ||||
| Status: | Peer Reviewed | ||||
| Publication Status: | Published | ||||
| Access rights to Published version: | Restricted or Subscription Access | ||||
| Funder: | Natural Sciences and Engineering Research Council of Canada (NSERC), Suomen Akatemia [Academy of Finland] |
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