Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation†

Oliver Turque; Ryan M. O'Connor; Alexander Greer

doi:10.1111/php.13727

journal article Oct 19, 2022

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation†

Oliver Turque

Ryan M. O'Connor

Alexander Greer

Photochemistry and Photobiology Vol. 99 No. 2 pp. 652-660 · Wiley

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Abstract

AbstractThe role of singlet oxygen potentially mediating increased conformational flexibility of a disulfide was investigated. Density functional theory (DFT) calculations indicate that the singlet oxygenation of 1,2‐dimethyldisulfane produces a peroxy intermediate. This intermediate adopts a structure with a longer S–S bond distance and a more planar torsional angleθ(C–S–S–C) compared with the nonoxygenated 1,2‐dimethyldisulfane. The lengthened S–S bond enables a facile rotation about the torsional angle in the semicircle region 0° < θ < 210°, that is ~5 kcal mol−1lower in energy than the disulfane. The peroxy intermediate bears nO → σS–Sand nO → σ*S–Sinteractions that stabilize the S–O bond but destabilize the S–S bond, which contrasts with stabilizing nS → σ*S–Shyperconjugative effects in the disulfane S–S bond. Subsequent departure of O2from the disulfane peroxy intermediate is reminiscent of peroxy intermediates which also expel O2, yet facilitatecis‐transisomerizations of stilbenes, hexadienes, cyanines, and carotenes. “Non‐oxidative”1O2interactions with a variety of bond types are currently underappreciated. We hope to raise awareness of how these interactions can help elucidate the origins of molecular twisting.

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Details

Published: Oct 19, 2022
Vol/Issue: 99(2)
Pages: 652-660
License: View

Authors

O

Oliver Turque

Department of Chemistry Brooklyn College, City University of New York New York NY; Ph.D. Program in Biochemistry The Graduate Center of the City University of New York New York NY

R

Ryan M. O'Connor

Department of Chemistry Brooklyn College, City University of New York New York NY

A

Alexander Greer

Department of Chemistry Brooklyn College, City University of New York New York NY; Ph.D. Program in Biochemistry The Graduate Center of the City University of New York New York NY; Ph.D. Program in Chemistry The Graduate Center of the City University of New York New York NY

Cite This Article

Oliver Turque, Ryan M. O'Connor, Alexander Greer (2022). Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation†. Photochemistry and Photobiology, 99(2), 652-660. https://doi.org/10.1111/php.13727

Singlet Oxygen's Potential Role as aNonoxidativeFacilitator of Disulfide S–S Bond Rotation†

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