Skeletal Scrambling of Sulfur Diimide Radical-Anions
by Bestari, Ketut T.; Oakley, Richard T.; Cordes, A. Wallace
In the presence of a catalytic quantity of alkali metal mixtures of sulphur diimides RNSNR and R'NSNR' (R, R' = Ph, 4-C6H4Me, 4-C6H4OMe, SiMe3, SPh) undergo a rapid scrambling of the R and R' groups. When R and R' are significantly different (e.g., R = Ph, R' = SiMe3 or SPh) the equilibrium is shifted to favour the unsymmetrical sulphur dimmide (R not-equal R'); the procedure thus represents an effective method for preparing such derivatives. A mechanism involving the centrosymmetric association and rearrangement of two sulphur diimide radical anions is suggested for the observed ligand scrambling. The synthesis and X-ray structure determination of the mixed diimide (4-NO2C6H4)SNSN(4-C6H4OMe) is reported. The crystals are monoclinic, space group P2(1)/n; the molecules stack as plates along the a axis in a head-to-head fashion, producing an interplanar spacing between consecutive S2N2 units of 3.421 angstrom.
- Canadian Journal of Chemistry-Revue Canadienne de Chimie
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- 1480-3291; 0008-4042