A density functional theory study is presented that provides the evidence that singlet oxygen has a path to engage in reversible bonding with RS–SR to promote rotation about the S–S bond. Mechanistic detail provided by this study reveals a singlet oxygen-induced conformational easing process, which enables greater flexibility prior to departure of molecular oxygen. The role of singlet oxygen in greater conformational flexibility from reversible interactions with alkenes and polyenes has been studied to some extent, but is seemingly overlooked with disulfides. Disulfides can allow for an addition of singlet oxygen to yield a persulfoxide [RSS(–+OO−)R] that in one path can lead to oxygen departure. Insight will be provided for conformation relaxation process about the S–S bond prior to this departure. Charge-transfer interactions of singlet oxygen with disulfides will also be discussed.

Mechanism of conformational flexibility at the disulfide bond: Role of singlet oxygen addition and elimination

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