A computational mechanistic study of the cleavage of sulfur-sulfur bond by Frustrated Lewis Pairs

In Silico Investigation of the Mechanism of Disulfide Bond Dissociation by New Frustrated Lewis Pairs

“…However, the activation energy barrier and reaction energy values are 1−3 kcal/mol higher than in the M06-2X/6-311G (d, p) level. Recently, Qin et al 32 studied the S−S activation in disulfides using a frustrated Lewis pair (FLP) consisting of ( t Bu) 3 P/ B(C 6 F 5 ) 3 . The calculated free energy of activation and reaction free energy were found to be 10 and −6 kcal/mol, respectively, in toluene solvent at the M06-2X/6-311G (d, p) level of theory calculation.…”

“…To check whether LA and LB can activate disulfide individually, we have studied the reaction by taking LA + disulfide and LB + disulfide separately. From the literature, it is evident that both Lewis acids and Lewis bases individually cannot cleave the S–S bond. However, conventional Lewis bases, such as phosphines, exhibit the ability to break the disulfide bond in the presence of water. , In contrast, Lewis acids tend to form donor–acceptor complexes with the disulfide, without actively splitting the S–S bond .…”

“…They found that the S−S bond of R−S− S−R (R = Ph or i Pr) could be readily cleaved by FLPs, such as ( t Bu) 3 P/B(C 6 F 5 ) 3 , under ambient conditions (25 °C, 1 atm), yielding thiophosphonium thioborate zwitterions. Recently, a detailed computational study of this disulfide cleavage reaction has been performed by Qin et al 32 In 2010, Alcarazo and coworkers discovered that the S−S bond could be heterolytically cleaved by a purely carbogenic FLP. 33 Zhou and co-workers 34 also demonstrated the heterolytic cleavage of the S−S bond in diphenyl disulfide by an FLP.…”

Insights into the Zintl Cluster Mediated Disulfide Bond Separation: A DFT Study

“…However, the S−S bond cleavage by phosphine is highly endothermic in gas phase and the endothermicity is dropped when water is added as explicit as well as implicit solvent correction model. Several studies in both experimental and computational shows that the disulfide bond can be cleaved by the frustrated Lewis pairs (FLP) [20–22] . Therefore, it is evident that nucleophile agent can be a great reagent for the disulfide bond cleavage.…”

“…Several studies in both experimental and computational shows that the disulfide bond can be cleaved by the frustrated Lewis pairs (FLP). [20][21][22] Therefore, it is evident that nucleophile agent can be a great reagent for the disulfide bond cleavage. In this regard, we thought of a new type of Lewis base i. e., Zintl Lewis base, which can also be used as a nucleophile in S N 2 reaction.…”