Can Superhalogen Ligand Make More Reactive Frustrated Lewis Pairs?

Abstract

New Frustrated Lewis Pairs (FLPs) are designed and are attempted to activate molecular hydrogen. The new FLPs are modeled by changing the ligands in the Lewis acid (LA) part of the TPFPB (Tris(pentafluorophenyl)borane) molecule. The modifications are done by replacing the phenyl group in TPFPB with three different aromatic heterocyclic ligands. The stability and reactivity of FLPs: [(C 2 BNSHF 2 )] 3 BÀ P( t Bu) 3 , [(C 2 BNSF 3 )] 3 BÀ P-( t Bu) 3 and [C 2 BNO(CN) 3 ] 3 BÀ P(tBu) 3 is analysed in terms of the dual descriptors, NBO/Hirshfeld charges, VDE, hardness (η) and electrophilicity (ω). Although all three modeled FLPs show their capability towards activating molecular hydrogen, the [C 2 BNO (CN) 3 ] 3 BÀ P( t Bu) 3 shows better performance than the conventionally used FLP: (C 6 F 5 ) 3 BÀ P( t Bu) 3 .

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

“…In this study, a novel frustrated Lewis pair (FLP) system has been designed, consisting of the bulky Lewis base P­( t Bu) 3 and the super Lewis acid B­(C 2 NBSHF 2 ) 3 . The Lewis acid, B­(C 2 NBSHF 2 ) 3 , is electron-deficient due to the presence of the superhalogen ligand, which enhances its Lewis acidity compared to the conventionally used Lewis acid B­(C 6 F 5 ) 3 . , Very recently, these types of superhalogen ligands have been synthesized experimentally . As discussed earlier, we have used P­( t Bu) 3 ···B­(C 2 NBSHF 2 ) 3 for the activation of the disulfide bond.…”

Insights into the catalytic activity of boron-doped thiazoles in the Diels–Alder reaction

“…[9][10][11][12][13] Looking at the role of BF 3 in this cycloaddition reaction, we can think about a special kind of molecule that can easily accept the electron, known as a superhalogen. [14][15][16][17][18][19][20][21][22][23][24][25] Superhalogen is a class of molecules with higher electron affinity than halogen. Superhalogen can also act as a superacid.…”

Insight into acrolein activation by P/B intramolecular frustrated Lewis pairs

“…Since then, numerous studies have investigated the activation of different small molecules, including CO 2 , CO, SO 2 , NO, N 2 O, H 2 O, etc., using frustrated Lewis pairs. [14][15][16][17][18][19][20][21][22][23][24][25] There have also been significant efforts towards the activation of di-nitrogen (N 2 ), 2,[26][27][28][29] as well as other strong bond activations, such as C-H, Si-H, C-F, etc. [30][31][32] New FLPs can be designed by modifying both the Lewis base and acid centers.…”

“…This pioneering work opened up potential applications of FLPs in hydrogenation reactions of various organic compounds such as imines, nitriles, alkenes, alkynes, and more. Since then, numerous studies have investigated the activation of different small molecules, including CO 2 , CO, SO 2 , NO, N 2 O, H 2 O, etc., using frustrated Lewis pairs 14–25 . There have also been significant efforts towards the activation of di‐nitrogen (N 2 ), 2,26–29 as well as other strong bond activations, such as C‐H, Si‐H, C‐F, etc 30–32 .…”