Density functional theory calculations on S―S bond dissociation energies of disulfides. (7th August 2015)

• Record Type: Journal Article
• Authors: Yang, Yi‐Meng; Yu, Hai‐Zhu; Sun, Xiao‐Hui; Dang, Zhi‐Min
• Is Part Of: Journal of physical organic chemistry. Volume 29:Number 1(2016)
• Page Start: 6
• Page End: 13
• Publication Date: 2015-08-07
• Subjects: DFT -- disulfides -- S―S bond dissociation energies -- substituent effect; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3480
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract: The S―Sbond cleavage plays an important role in affecting the reactivity or biological activities of disulfide‐based compounds. With the aid of density functional theory (DFT) calculations, the present study focuses on predicting the S―S bond dissociation energies (BDEs) of disulfides. The range of BDEs of different types of disulfides was constructed for the first time. It was found that the electronic effect (and especially the conjugation effect) of substituents is predominant in determining the S―S bond strength of disulfides. By contrast, the steric effect is insignificant for most molecules due to the long S―S bond distances. We hope that the present study will benefit the future development of more powerful strategies in activating the S―S bond of disulfides. Copyright © 2015 John Wiley & Sons, Ltd. Abstract : The S‐S bond dissociation energies of different types of disulfides has been evaluated by density functional theory (M06‐2X) calculations.