The Beckmann rearrangement in the framework of reaction electronic flux

Giri, Santanab; Inostroza-Rivera, Ricardo; Jana, Madhurima

doi:10.1007/s00214-016-2025-3

Cited by 9 publications

(10 citation statements)

References 32 publications

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“…To gain more insights into the electronic activity, two more reactivity descriptors, electronic flux for the nucleophilic process (electrophilic attack) J N (ξ) and electronic flux for the electrophilic process (nucleophilic attack) J E (ξ), have been generated based on the reaction electronic flux J (ξ). J N (ξ) and J E (ξ) are defined as the negative derivative of HOMO (ε H ) and LUMO (ε L ) respectively, along the reaction coordinate . Therefore, the following expressions can be derived from eq J false( ξ false) ≅ − d true( E normalL normalU normalM normalO + E normalH normalO normalM normalO 2 true) d ξ J false( ξ false) = − 1 2 true( normald ε normalH normald ξ true) − 1 2 true( normald ε normalL normald ξ true) = J N + J E …”

Section: Methodsmentioning

confidence: 99%

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

Sinha,

Giri

2023

J. Phys. Chem. A

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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( t Bu) 3 /B(C 2 NBSHF 2 ) 3 can also be used like the conventional FLP ( t Bu) 3 P/B(C 6 F 5 ) 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.

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Section: Methodsmentioning

confidence: 99%

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

Sinha,

Giri

2023

J. Phys. Chem. A

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“…To explore the electronic activity in detail, i.e., whether the reaction is nucleophilic or electrophilic, the REF can also be separated in terms of nucleophilic reactivity flux J N (x) and electrophilic reactivity flux J E (x) along the IRC. 62 Therefore, the reaction electronic flux can be expressed in terms of J N (x) and J E (x) as…”

Section: Computational Detailsmentioning

confidence: 99%

“…, whether the reaction is nucleophilic or electrophilic, the REF can also be separated in terms of nucleophilic reactivity flux J N ( ξ ) and electrophilic reactivity flux J E ( ξ ) along the IRC. 62 Therefore, the reaction electronic flux can be expressed in terms of J N ( ξ ) and J E ( ξ ) as J ( ξ ) = J N ( ξ ) + J E ( ξ )where J N ( ξ ) and J E ( ξ ) are defined as the negative derivatives of HOMO and LUMO, respectively, along the reaction coordinate, ξ .…”

Section: Computational Detailsmentioning

confidence: 99%

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

Sinha¹,

Das²,

Giri³

2023

Phys. Chem. Chem. Phys.

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“…After having the physical interpretation of the alkylation reaction in both solvents, a thorough investigation has been performed to analyze the electronic activity throughout the reaction pathway by calculating the reaction electronic flux, J(ξ). J(ξ) is found to be a reliable descriptor [43][44][45][46][47]55 for accounting for the electronic activity, and according to its interpretation, a zero J(ξ) profile indicates no additional electronic activity besides the equilibrium or basal activity. A positive J(ξ) indicates the electronic activity is associated with the bond formation or strengthening process, whereas the reverse is true for a negative J(ξ) profile.…”

Section: ■ Computational Detailsmentioning

confidence: 99%

“…In addition, J (ξ) has also been separated into two parts based on the highest occupied and the lowest unoccupied frontier molecular orbitals, HOMO and LUMO, as . Here, J N (ξ) is the reaction electronic flux associated with nucleophilic reactivity and J E (ξ) is the REF responsible for electrophilic reactivity. , A dual descriptor − ( Δf(r) ) has also been calculated to determine the electrophilic and nucleophilic regions inside the molecule. All of the reactions are carried out using two different solvents, H 2 O and THF.…”

Section: Computational Detailsmentioning

confidence: 99%

Density Functional Treatment on Alkylation of a Functionalized Deltahedral Zintl Cluster

et al. 2020

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Density functional theory (DFT) is one of the popular methods to understand the electronic structure of molecular systems based on electronic density. On the basis of this theory, several conceptual DFT descriptors have been developed which can deal with the stability, reactivity, and several other physicochemical properties of molecules. Here, we have taken a nine-atom-functionalized deltahedral Zintl cluster of germanium (Ge) to examine the alkylation reaction mechanism. The study showed that the Zintl cluster having a methyl group as a ligand, [Ge9(CH3)3 –], acts as a better nucleophile than the cyanide (−CN)-substituted cluster [Ge9(CN)3 –] in terms of different thermodynamic parameters like free energy, enthalpy of activation, reaction energy, etc. A detailed reaction electronic flux analysis reveals the nature of the electronic activity throughout the reaction pathway. The reaction force, Wiberg bond indices, and dual descriptor lend additional support to the reaction mechanism. It has been found that the alkylation reaction between the Zintl ion and the alkyl halide follows a SN2-like mechanism.

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The Beckmann rearrangement in the framework of reaction electronic flux

Cited by 9 publications

References 32 publications

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

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

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

Density Functional Treatment on Alkylation of a Functionalized Deltahedral Zintl Cluster

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