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

Understanding the mechanism of disulfide bond cleavage is important in various scientific disciplines including organic synthesis, catalysis, and biochemistry. In this study, an in silico investigation has been carried out for the dissociation of disulfide bonds using newly designed frustrated Lewis pairs (FLPs). The study revealed that the cleavage of the disulfide bond by the FLP P(^tBu)₃/B(C₂NBSHF₂)₃ can also be used like the conventional FLP (^tBu)₃P/B(C₆F₅)₃. It has been observed that the reaction is almost thermoneutral in the gas phase but exothermic in nonpolar solvents, such as toluene, heptane, and hexane. Furthermore, the natural bond orbital (NBO) describes insights into the role of FLPs in facilitating this reaction. Additionally, reaction force and force constant studies shed light on the energy requirements for completing the reaction and the synchronous nature of the dissociation process, respectively. Reaction electronic flux (REF) and its separations give the pattern of electronic activity during the chemical reaction. Extended transition state-natural orbitals for chemical valence (ETS-NOCV) and principal interacting orbital (PIO) analysis provide valuable information about the orbital interactions during the chemical reaction.