Issue 2, 1999

UV-vis and IR spectroscopic characterization of diphenyl disulfide radical cation in acid zeolites and its rearrangement to thianthrenium radical cation

Abstract

Adsorption of diphenyl disulfide (DPDS) from CH2Cl2 solutions onto acid zeolites at room temperature generated the “extended” radical cation, DPDS˙+. At loadings of 3 wt%, oxidation to DPDS˙+ is essentially complete. Upon heating the loaded zeolite to 200 °C, the adsorbed DPDS˙+ was converted into thianthrenium radical cation (TH˙+). Ab initio calculations at the B3LYP and HF levels using the 6-31G* basis set suggest cyclization of a diphenyl disulfide-S,S-dication as a reasonable rate-determining step of the conversion. Non-acidic zeolites devoid of Lewis and Brønsted sites (as determined by the pyridine adsorption–desorption method) failed to generate DPDS˙+ to an extent detectable spectroscopically; these results support Lewis and/or Brønsted sites as being responsible for the observed oxidation.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1999, 145-152

UV-vis and IR spectroscopic characterization of diphenyl disulfide radical cation in acid zeolites and its rearrangement to thianthrenium radical cation

V. Martí, L. Fernández, V. Fornés, H. García and H. D. Roth, J. Chem. Soc., Perkin Trans. 2, 1999, 145 DOI: 10.1039/A806522E

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