PIO and IBO analysis to unravel the hidden details of the CO<sub>2</sub> sequestration mechanism of aromatically tempered N/B-based IFLPs

Faizan, Mohmmad; Kumar, Adarsh; Raghasudha, Mucherla; Pawar, Ravinder

doi:10.1039/d3cp02928j

Cited by 3 publications

(1 citation statement)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Their ability to activate small molecules under mild conditions, along with their tunable reactivity, makes them valuable tools in synthetic chemistry, providing greener and more sustainable routes to various chemical transformations. [6][7][8][9] A number of theoretical studies have been carried out to explain and predict the reactivity of intermolecular [10][11][12] and intramolecular [13][14][15][16][17][18][19][20][21][22][23] reactions involving FLPs.…”

Section: Introductionmentioning

confidence: 99%

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO₂‐Sequestration

Ferrer,

Alkorta,

Elguero

et al. 2024

ChemPhysChem

View full text Add to dashboard Cite

The isolated (pyridin‐2‐ylmethyl)triel derivatives (triel = B, Al and Ga) show an intramolecular N···Tr triel bond as shown by compounds found in the Cambridge Structural Database and DFT calculations. The possibility to use them as masked frustrated Lewis pairs (mFLP) has been explored theoretically concerning their reaction with CO2. The adduct formation proceeds in two steps. In the first one, the (pyridin‐2‐ylmethyl)triel derivatives break the intramolecular N···Tr bond assisted by CO2 and in the second step the adduct is formed with Tr‐O and N‐C covalent bonds. The corresponding energy minima and transition states (TS) of the reaction have been characterized and analyzed. The distortion/interaction model analysis of the stationary points indicates that the whole process can be divided in two parts: reorganization of the mFLP in the first steps of the reaction while the reaction with CO2 (associated to the distortion of this molecule) is more important in the formation of the final adduct. In all cases studied, the final products are more stable than the starting molecules that combine with reasonable TS energies indicate that these reactions can occur.

show abstract

Section: Introductionmentioning

confidence: 99%

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO₂‐Sequestration

Ferrer,

Alkorta,

Elguero

et al. 2024

ChemPhysChem

View full text Add to dashboard Cite

show abstract

Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO₂ Into Valuable Chemicals

Faizan,

Santhosh,

Chakraborty

et al. 2024

J of Physical Organic Chem

View full text Add to dashboard Cite

The conversion of CO2 into valuable chemicals remains a significant challenge for achieving environmental sustainability, primarily due to the stability of the CO2 molecule. This necessitates the development of efficient and ecofriendly catalysts. In recent years, frustrated Lewis pairs (FLPs) have shown promise for CO2 utilization. In this study, we introduce α‐aminodiboronic acid (DBA), a novel trifunctional aminoboronic acid, as an intramolecular FLP for converting CO2 into cyclic carbonate and formic acid. Using density functional theory (DFT) calculations, we explored the reaction mechanism and investigated DBA's electronic structure through molecular electrostatic potential surface (MESP) and natural bond orbital (NBO) analyses. Our results reveal that one −B (OH)2 group induces an unusual state of frustration in the molecule due to charge transfer from the nitrogen atom's lone pair to the π* orbitals, enhancing catalytic performance. The additional −B (OH)2 group serves as an anchoring site for reactive species. The epoxide activation energy is reduced by approximately 27 kcal/mol compared to the uncatalyzed reaction, and the reduction of CO2 occurs with a requirement of 26 kcal/mol. The additional −B (OH)2 plays a crucial role in the catalytic mechanism and minimizes the energies of various structures observed in the reaction path. The reaction energetics align with structural analysis observations, marking this study as the first report on single‐molecule trifunctional FLPs for transforming CO2 into valuable chemicals.

show abstract

Orbital and free energy landscape expedition towards the unexplored catalytic realm of aromatically modified FLPs for CO₂ sequestration

Faizan,

Chakraborty,

Bana

et al. 2024

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

PIO and IBO analysis to unravel the hidden details of the CO₂ sequestration mechanism of aromatically tempered N/B-based IFLPs

Abstract: The PIO and IBO analysis shows the asynchronicity in the CO2 activation mechanism by aromatically enhanced N/B based Frustrated Lewis Pairs (FLPs).

Cited by 3 publications

References 68 publications

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO₂‐Sequestration

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO₂‐Sequestration

Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO₂ Into Valuable Chemicals

Orbital and free energy landscape expedition towards the unexplored catalytic realm of aromatically modified FLPs for CO₂ sequestration

Contact Info

Product

Resources

About

PIO and IBO analysis to unravel the hidden details of the CO2 sequestration mechanism of aromatically tempered N/B-based IFLPs

Abstract: The PIO and IBO analysis shows the asynchronicity in the CO2 activation mechanism by aromatically enhanced N/B based Frustrated Lewis Pairs (FLPs).

Cited by 3 publications

References 68 publications

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO2‐Sequestration

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO2‐Sequestration

Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO2 Into Valuable Chemicals

Orbital and free energy landscape expedition towards the unexplored catalytic realm of aromatically modified FLPs for CO2 sequestration

Contact Info

Product

Resources

About

PIO and IBO analysis to unravel the hidden details of the CO₂ sequestration mechanism of aromatically tempered N/B-based IFLPs

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO₂‐Sequestration

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO₂‐Sequestration

Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO₂ Into Valuable Chemicals

Orbital and free energy landscape expedition towards the unexplored catalytic realm of aromatically modified FLPs for CO₂ sequestration