81260-54-0Relevant articles and documents
15N NMR study of the oxidation of the trisulfur trinitride anion by molecular oxygen: A comparison of the molecular and electronic structures of the S3N3-, S3N3O-, and S3N3O2- ions
Chivers, Tristram,Cordes, A. Wallace,Oakley, Richard T.,Pennington, William T.
, p. 2429 - 2435 (2008/10/08)
The oxidation of the S3N3- ion in acetonitrile solution by molecular oxygen gives rise to four major products: S4N5-, S4N5O-, S3N3O-, and S3N3O2-. The relative yields of these species are a function of the flow rate of oxygen, and the progress of the reaction and the structure of the various ions in solution can be analyzed by using 15N NMR spectroscopy (and 15N-labeled S3N3-). The crystal and molecular structures of (Ph3P)2N+S3N3O - and (Ph3P)2N+S3N3O 2- have been determined by X-ray diffraction. Crystals of the former are monoclinic, space group P21/c, with a = 17.161 (2) ?, b = 9.970 (1) ?, c = 20.591 (2) ?, β = 104.45(1)°, V = 3411.7 ?3, and Z = 4. Crystals of the latter are monoclinic, space group P21, with a = 12.421 (1) ?, b = 13.036 (1) ?, c = 10.699 (1) ?, β = 103.36 (1)°, V = 1685.6 ?3, and Z = 2. Both structures were solved by direct methods and refined by full-matrix least-squares procedures; for (Ph3P)2N+S3N3O - the final R = 0.053 and Rw = 0.075 for 3058 reflections with I > 3σ(I), and for (Ph3P)2N+S3N3O 2- the final R = 0.048 and Rw = 0.057 for 2312 reflections with I > 3σ(I). The two anions S3N3O- and S3N3O2- both possess six-membered S3N3 ring structures with exocyclic oxygen atoms bonded to sulfur (in S3N3O2- the oxygens are geminally substituted). Both rings exhibit significant variations in chemically equivalent bond lengths and angles. The visible spectra of S3N3O- (λmax = 509 and 340 nm) and S3N3O2- (λmax = 562 and 362 nm) are interpreted in terms of the expected perturbations on the π-manifold of the S3N3- anion; the observed absorptions are assigned to π* → π* type excitations.
