Structural Studies Provide Insight on the Fate of 1,5-Dithiacanes: Two Electron Reversible Oxidation versus Irreversible Oxidation

Authors

• Richard S. Glass, University of Arizona
• Sanaullah Khan, University of Kansas - Lawrence
• Michael D. Ryan, Marquette UniversityFollow
• Mahmood Sabahi, University of Arizona
• Edward D. Lorance, University of Arizona
• Riasat M. Mobashar, University of Arizona
• Waheguru P. Singh, University of Arizona
• George S. Wilson, University of Kansas - Lawrence

Document Type

Article

Publication Date

1-2026

Publisher

American Chemical Society

Source Publication

Journal of Organic Chemistry

Source ISSN

0022-3263

Abstract

Synthesis and chemical/electrochemical properties of a conformationally constrained 1,5-dithiocane -3,7-dithiatricyclo[6.4.0.0^2,10.0^9,11]dodecane (norDTCO) is described. Density function theory (DFT) was used to calculate the structures of the neutral norDTCO, the radical cation norDTCO^+●, and the dication norDTCO²⁺ to investigate the importance of orbital orientations in the oxidation mechanism. Results of the first oxidation were consistent with a 2-center-3-electron (2c-3e) bonding interaction between the sulfur atoms in the radical cation. Results of the second oxidation were consistent with a transannular S–S σ-bond in the dication. In acetonitrile, the electrochemical oxidation was consistent with an apparent two-electron oxidation of norDTCO in a single wave, which was nearly reversible at slow scan rates. Similar to the oxidation of 1,5-dithia cylooctane (DTCO) to DTCO²⁺, norDTCO²⁺ was consistent with the formation of a ⁺S–S⁺ σ-bond as predicted by DFT calculations. DFT calculations of various constrained and unconstrained 1,5-dithiacanes were used to identify conditions where neighboring group participation was important and where a reversible two-electron oxidation/reduction wave could occur. However, in dichloromethane, two one-electron waves were observed, which indicates that in dichloromethane a transannular ⁺S–S⁺ σ-bond was not formed.

Comments

Accepted version. The Journal of Organic Chemistry, Vol. 91, No. 4 (January 2026): 1473-1484. DOI. © 2026 American Chemical Society. Used with permission.

Recommended Citation

Glass, Richard S.; Khan, Sanaullah; Ryan, Michael D.; Sabahi, Mahmood; Lorance, Edward D.; Mobashar, Riasat M.; Singh, Waheguru P.; and Wilson, George S., "Structural Studies Provide Insight on the Fate of 1,5-Dithiacanes: Two Electron Reversible Oxidation versus Irreversible Oxidation" (2026). Chemistry Faculty Research and Publications. 1111.
https://epublications.marquette.edu/chem_fac/1111