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Absorption of SO2(g) by TDAE[O2SSO2](s) to Give TDAE[O2SS(O)2SO2](s): Related Reactions of [NR4]2[O2SSO2](s) (R = CH3, C2H5).
Decken, Andreas; Greer, Scott; Grein, Friedrich; Mailman, Aaron; Mueller, Birgit; Paulose, Tressia A P; Passmore, Jack; Rautiainen, J Mikko; Richardson, Stephanie A; Schriver, Melbourne J; Whidden, Thomas K.
Affiliation
  • Decken A; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Greer S; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Grein F; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Mailman A; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Mueller B; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Paulose TA; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Passmore J; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Rautiainen JM; Laboratory of Inorganic Chemistry, University of Oulu , P.O. Box 3000, Oulu 90014, Finland.
  • Richardson SA; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
  • Schriver MJ; Department of Chemistry, Crandall University , P.O. Box 6004, Moncton, New Brunswick E1C 0L7, Canada.
  • Whidden TK; Department of Chemistry, University of New Brunswick , Fredericton, New Brunswick E3B 5A3, Canada.
Inorg Chem ; 55(12): 5999-6009, 2016 Jun 20.
Article in En | MEDLINE | ID: mdl-27276103
ABSTRACT
One mole equivalent of gaseous SO2 is absorbed by purple TDAE[O2SSO2](s), producing red, essentially spectroscopically pure TDAE[O2SS(O)2SO2](s); under prolonged evacuation, the product loses SO2(g), regenerating TDAE[O2SSO2](s). Similarly, [NR4]2[O2SS(O)2SO2](s) (R = Et, Me) can be prepared, albeit at lower purity, from the corresponding tetraalkylammonium dithionites (prepared by a modification of the known [NEt4]2[O2SSO2](s) preparation). While the [NEt4](+) salt is stable at rt; the [NMe4](+) salt has only limited stability at -78 °C. Vibrational spectra assignments for the anion in these salts were distinctly different from those for the anion in salts containing the long-known [O3SSSO3](2-) dianion, the most thermodynamically stable form of [S3O6](2-) (we prepared TDAE[O3SSSO3]·H2O(s) and obtained its structure by X-ray diffraction and vibrational analyses). The best fit between the calculated ((B3PW91/6-311+G(3df) and PBE0/6-311G(d)) and experimental vibrational spectra were obtained with the dianion having the [O2SS(O)2SO2](2-) structure. Vibrational analyses of the three [O2SS(O)2SO2](2-) salts prepared in this work showed that the corresponding [O3SSO2](2-) salts were present as a ubiquitous decomposition product. The formation of these new [O2SS(O)2SO2](2-) dianion salts was predicted to be favorable for [NMe4](+) and larger cations using a combination of theoretical calculations (B3PW91/6-311+G(3df)) and volume based thermodynamics (VBT). Similar methods accounted for the greater stabilities of the TDAE(2+) and [NEt4](+) salts of [O2SS(O)2SO2](2-) compared to [NMe4]2[O2SS(O)2SO2](s) toward irreversible decomposition to the corresponding [O3SSO2](2-) salts. These salts represent the first known examples of a new class of poly(sulfur dioxide) dianion, [SO2]n(2-) in which n > 2.

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Inorg Chem Year: 2016 Document type: Article Affiliation country: Canada

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Inorg Chem Year: 2016 Document type: Article Affiliation country: Canada