Small molecule activation and dehydrogenation of an amine–borane system using frustrated Lewis pairs

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

doi:10.1007/s11224-022-01934-y

Cited by 11 publications

(11 citation statements)

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“…In general, for aromatic molecules, the clockwise (diatropic) current is present outside the ring, and the anticlockwise current (paratropic) is present inside the ring. In previous works [78–82], we have shown that it is a compelling technique for the analysis of aromaticity. Here also, we have employed the GIMIC method to calculate the ring current across various bonds at the TS structures of all four reactions (Table 5, Figure 8).…”

Section: Resultsmentioning

confidence: 99%

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Local reactivity descriptors of the important atoms in chelotropic reactions provide insight into their global variants along the reaction path

Sánchez‐Márquez

Mondal

Patra

et al. 2023

Int J of Quantum Chemistry

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Chelotropic reactions are widely used in organic synthesis. These reactions are of the pericyclic type where a π bond and a lone pair are transformed into a pair of sigma bonds; with both sigma bonds added to the same atom. This work presents an analysis of several representative chelotropic reactions. To study the reaction path, we have divided it into two parts, from the reactants to the transition state and from the transition state to the products which has allowed us to compare the behavior of the reactants in these two ranges of the path. To perform the analysis, global reactivity descriptors based on the conceptual‐density functional theory (DFT), such as electrophilicity and global softness, have been calculated. To analyze these descriptors, the corresponding local descriptors have been used. A model based on Sanderson's principle (electronegativity equalization principle), developed previously, has been used to calculate the local reactivity descriptors (atomic). The statistical methodology of multiple regression analysis has been used to determine which local variables are the most relevant for the global parameter under study (softness, and electrophilicity), also the principal component analysis has been used as a guide to estimate the number of variables to take into account in the analysis, finally this has led us to important correlations between global and local parameters which has allowed us to analyze the reactions of the study. Transition states of the reactions are aromatic as obtained from the nucleus independent chemical shift (NICS) and gauge including magnetically induced ring current (GIMIC) analysis.

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Section: Resultsmentioning

confidence: 99%

“…In previous works [78][79][80][81][82], we have shown that it is a compelling technique for the analysis of aromaticity. Here also, we have employed the GIMIC method to calculate the ring current across various bonds at the TS structures of all four reactions (Table 5, Figure 8).…”

Section: Analysis Of Transition State Aromaticitymentioning

confidence: 99%

Local reactivity descriptors of the important atoms in chelotropic reactions provide insight into their global variants along the reaction path

Sánchez‐Márquez

Mondal

Patra

et al. 2023

Int J of Quantum Chemistry

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“…Since, both the NICS(0) and NICS(1zz) values are gradually diminished as the reaction progress, i.e., the antiaromaticity of the rings, is decreased because of H 2 activation. Therefore, reduction of antiaromaticity 69 is responsible for boosting up the reactivity of these FLPs.…”

Section: Aromaticity-assisted Reactivity Of Flpmentioning

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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“…Aromaticity is one of the most fundamental concepts in chemistry, 1 which can not only bring the thermodynamic stability of species but also drive some reactions. [2][3][4][5][6][7][8][9] Thus, it has been attracting increasing attention from both experimental and theoretical chemists. The resonance structure of the benzene ring was proposed by Kekulé in 1865, which is important for understanding its aromaticity.…”

Section: Introductionmentioning

confidence: 99%