Unveiling novel reactivity of P/Al frustrated Lewis pair: ring size-dependent activation of cyclic ethers/thioethers and CO2 insertion therein

Mondal, Himangshu; Patra, Subrata; Chattaraj, Pratim Kumar

doi:10.1007/s12039-022-02119-0

Cited by 6 publications

(5 citation statements)

References 90 publications

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“…The reduction of aldehydes and ketones into alcohols by way of hydrogenation is also possible in nonpolar solvents by utilizing B(C 6 F 5 ) 3 /cyclodextrin FLP . In addition, FLP can reduce some other polar substrates like enamenes, cyclic ethers, enons, oximes, silyl enol ethers, etc. − …”

Section: Catalytic Hydrogenationmentioning

confidence: 99%

Frustrated Lewis Pairs: Bonding, Reactivity, and Applications

et al. 2023

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The outstanding capability of Frustrated Lewis Pair (FLP) catalysts to activate small molecules has gained significant attention in recent times. Reactivity of FLP is further extended toward the hydrogenation of various unsaturated species. Over the past decade, this unique catalysis concept has been successfully expanded to heterogeneous catalysis as well. The present review article gives a brief survey on several studies on this field. A thorough discussion on quantum chemical studies concerning the activation of H 2 is provided. The role of aromaticity and boron−ligand cooperation on the reactivity of FLP is discussed in the Review. How FLP can activate other small molecules by cooperative action of its Lewis centers is also discussed. Further, the discussion is shifted to the hydrogenation of various unsaturated species and the mechanism regarding this process. It also discusses the latest theoretical advancements in the application of FLP in heterogeneous catalysis across various domains, such as two-dimensional materials, functionalized surfaces, and metal oxides. A deeper understanding of the catalytic process may assist in devising new heterogeneous FLP catalysts through experimental design.

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Section: Catalytic Hydrogenationmentioning

confidence: 99%

Frustrated Lewis Pairs: Bonding, Reactivity, and Applications

et al. 2023

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“…In 2006, since the breakthrough discovery of reversible hydrogen splitting using an intramolecular P/B frustrated Lewis pair (FLP) by Stephan et al, 17 both experimental and theoretical chemists devoted themselves to harnessing FLPs to activate various small molecules. [18][19][20][21][22][23][24][25] It is essential to highlight that while several FLPs were tried for this purpose, only a handful showed reversible H 2 activation.…”

Section: Introductionmentioning

confidence: 99%

CO₂ reduction using aluminum hydride: Generation of in‐situ frustrated Lewis pairs and small molecule activation therein

Mondal,

Chattaraj

2024

J Comput Chem

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CO2 reduction is appealing for the long‐term production of high‐value fuels and chemicals. Herein, using density functional theory (DFT) based calculations, we study the CO2 reduction pathway to formic acid using aluminum hydride and phosphine derivatives. Our primary focus is on aluminum hydride derivatives, aimed at improving the efficiency of the CO2 reduction process. Substituents with σ‐donating properties at the aluminum center are discovered to lower the activation barriers. We demonstrate how di‐tert‐butylphosphine oxide (LB‐O)/di‐tert‐butylphosphine sulfide (LB‐S)/di‐tert‐butylphosphanimine (LB‐N) work together with aluminum hydride to facilitate CO2 reduction process and generate in‐situ frustrated Lewis pairs (FLPs), such as FLP‐O, FLP‐S, and FLP‐N. The activation strain model (ASM) analysis reveals the significance of strain energy in determining activation barriers. EDA‐NOCV and PIO analyses elucidate the orbital interactions at the corresponding transition states. Furthermore, the study delves into the activation of various small molecules, such as dihydrogen, acetylene, ethylene, carbon dioxide, nitrous oxide, and acetonitrile, using those in‐situ generated FLPs. The study highlights the low activation barriers and emphasizes the potential for small molecule activation in this context.

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“…In the last 17 years, considerable advancements in catalytic hydrogenation using a plethora of FLPs and a variety of substrates have been achieved. 11,[27][28][29][30][31][32][33] In most cases, the mechanism involves first the protonation of the substrate followed by the hydride transfer from the LA center to give the reduced hydrogenated target molecule.…”

Section: Introductionmentioning

confidence: 99%

“…Ever since the discovery of H 2 activation by FLPs, the hydrogenation reaction of various species such as imines, 6,10,11 enamines, 12 ketones, 6,13–15 alkenes, 6,16,17 alkynes, 6,17,18 and CO 2 , 19–26 have been studied. In the last 17 years, considerable advancements in catalytic hydrogenation using a plethora of FLPs and a variety of substrates have been achieved 11,27–33 . In most cases, the mechanism involves first the protonation of the substrate followed by the hydride transfer from the LA center to give the reduced hydrogenated target molecule.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric catalysis by chiral FLPs: A computational mini‐review

Patra

2024

Chirality

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Steric hindrance in Lewis acid (LA) and Lewis base (LB) obstruct the Lewis acid–base adduct formation, and the pair was termed as frustrated Lewis pair (FLP). In the past 16 years, the field of enantioselective catalysis by chiral FLPs has been slowly growing. It was shown that chiral LAs are significant as they are involved in the hydrogen transfer (HT) step to the imine, resulting in enantioselectivity. After H2 activation, the borohydride can exist in a number of plausible conformations and their stability is governed by the presence of noncovalent interaction through C–H····π and π····π interactions. However, LBs are not ideal for asymmetric induction as they compete with the imine substrate as a counter LB. Further, the proton transfer from chiral LB to the imine does not induce any chirality as chirality develops in the HT step. However, intramolecular FLPs with chiral scaffold are very efficient as they possess an optimum distance between LA and LB, which facilitates the H2 activation but precludes the adduct formation of the small molecules substrate with the LA component. This mini‐review summarizes computational investigation involving chiral LA and LB, and discusses intramolecular FLPs in the enantioselective catalysis.

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Unveiling novel reactivity of P/Al frustrated Lewis pair: ring size-dependent activation of cyclic ethers/thioethers and CO2 insertion therein

Cited by 6 publications

References 90 publications

Frustrated Lewis Pairs: Bonding, Reactivity, and Applications

Frustrated Lewis Pairs: Bonding, Reactivity, and Applications

CO₂ reduction using aluminum hydride: Generation of in‐situ frustrated Lewis pairs and small molecule activation therein

Asymmetric catalysis by chiral FLPs: A computational mini‐review

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Unveiling novel reactivity of P/Al frustrated Lewis pair: ring size-dependent activation of cyclic ethers/thioethers and CO2 insertion therein

Cited by 6 publications

References 90 publications

Frustrated Lewis Pairs: Bonding, Reactivity, and Applications

Frustrated Lewis Pairs: Bonding, Reactivity, and Applications

CO2 reduction using aluminum hydride: Generation of in‐situ frustrated Lewis pairs and small molecule activation therein

Asymmetric catalysis by chiral FLPs: A computational mini‐review

Contact Info

Product

Resources

About

CO₂ reduction using aluminum hydride: Generation of in‐situ frustrated Lewis pairs and small molecule activation therein