Computational insights into the reactivity for the [2+5] cycloaddition reactions of norbornene-linked group 14 element/P-based and Si/group 15 element-based frustrated Lewis pairs with benzaldehyde

Su, Ming‐Der

doi:10.1039/d2cp05135d

Cited by 3 publications

(2 citation statements)

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“…We have employed theoretical research methods to comprehend the chemical reactions and intrinsic bonding properties of various intramolecular FLPtype molecules and small molecules, including H 2 , 64,65 CO 2 , 66,67 CS 2 , 68 tetrahydrofuran, 69 and ketones. 70 The objective of this study was to investigate the physical origin and bonding characteristics of the activation barriers that govern the binding reactions in the chemical interaction between a cyclohexane-linked molecule assisted by FLP and SO 2 . The study employed theoretical research methods to analyze two chemical reactions (eqs 1 and 2) as representative model systems.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, we employed the aforementioned experimental results as a template to investigate the effect of the same group of chemical elements on the reactivity of 1,2-cyclohexylene-linked intramolecular G13/G15-assisted (G13 = group 13 element and G15 = group 15 element) FLPs to capture SO 2 theoretically. We have employed theoretical research methods to comprehend the chemical reactions and intrinsic bonding properties of various intramolecular FLP-type molecules and small molecules, including H 2 , , CO 2 , , CS 2 , tetrahydrofuran, and ketones …”

Section: Introductionmentioning

confidence: 99%

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Reactivity of the Intramolecular Vicinal Group-13/P- and B/Group-15-Based Frustrate Lewis Pairs with Sulfur Dioxide: Mechanistic Insight from DFT

Zhang,

2023

Inorg. Chem.

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The emission of SO2 gas by industrialized societies contributes to the occurrence of acid rain in natural environments. In this study, we put forward a theoretical investigation into the capture reactions of SO2. Our analysis centers on the energy profiles of intramolecular 1,2-cyclohexylene-bridged FLP-associated molecules. We will particularly examine the reactions involving G13/P-based (with G13 denoting Group 13 element) and B/G15-based (with G15 representing Group 15 element) FLP-associated molecules. Except for Tl/P-FLP, B/N-FLP, and B/Bi-FLP, our theoretical examinations indicate that the remaining six FLP-associated molecules, namely G13′/P-FLP (G13′ = B, Al, Ga, and In) and B/G15 ′ -FLP (G15′ = P, As, and Sb), can easily undergo SO2 capture reactions due to their energetic feasibility. Particularly, our theoretical findings suggested that 1,2-cyclohexylene-bridged Al/P-FLP, Ga/P-FLP, B/As-FLP, and B/Sb-FLP are capable of undergoing a reversible reaction and returning to the initial reactant state. Our theoretical evidence indicates that the G13–G15 bond length in the 1,2-cyclohexylene-linked G13/G15-FLP can serve as a basis for evaluating the free activation barrier associated with its reaction with SO2. Two theoretical methods, namely, the frontier molecular orbital theory and the energy decomposition analysis-natural orbitals of chemical valence approach, are utilized to investigate the electronic structure and bonding nature of the reactions under consideration. Moreover, the analyses based on the activation strain model revealed that it is the geometrical deformation energies of G13/G15-FLP, which is the key factor that greatly influences the activation barriers of such SO2 capture reactions. Further, our theoretical computations indicate that such capturing reactions of SO2 by intramolecular 1,2-cyclohexylene-linked G13/G15-based FLP-type molecules obey the Hammond postulate.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reactivity of the Intramolecular Vicinal Group-13/P- and B/Group-15-Based Frustrate Lewis Pairs with Sulfur Dioxide: Mechanistic Insight from DFT

Zhang,

2023

Inorg. Chem.

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Investigating the Reactivity of Removing a Sulfur Atom from Propylene Sulfide with a Geminal Frustrated Lewis Pair and the Origin of Their Activation Barriers

Wu,

2024

Organometallics

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Using density functional theory (B3LYP-D3(BJ)/def2-TZVP), we explored the origin of the reaction barriers and reactivity for the elimination of one sulfur atom from propylene sulfide by methylene-linked geminal intramolecular G13/G15-based (G13 = group 13 element and G15 = group 15 element) frustrated Lewis pair (FLP) molecules. In contrast to the traditional understanding validated by previous theoretical examinations, our B3LYP computational results demonstrate that the elimination reactions with intramolecular geminal FLP-type molecules in this study proceed through multiple steps rather than a one-step concerted process. Our B3LYP computations reveal that during the multistep process the second transition state, G13/G15-TS2, serves as the rate-determining step, featuring a nucleophilic attack by the Lewis base at the G15 center on the least hindered sulfur atom of propylene sulfide, leading to the release of a propylene molecule. Based on our theoretical investigations using the activation strain model, the activation barrier of the essential second transition step is primarily determined by the structural deformation energy of the intramolecular geminal G13/G15-type FLP fragment, characterized by its flexible linear bent structure, as opposed to the rigid structure of the propylene sulfide fragment.

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Understanding the CO capture reaction through electronic structure analysis of four-membered-ring group-13/N- and B/group-15-based Lewis acid–base pairs

Zhang,

2024

RSC Adv.

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Computational insights into the reactivity for the [2+5] cycloaddition reactions of norbornene-linked group 14 element/P-based and Si/group 15 element-based frustrated Lewis pairs with benzaldehyde

Abstract: The element effects of Lewis acid (LA) and Lewis base (LB) on the potential energy surfaces of [2 + 5] cycloaddition reactions of norbornene-based G14/P-Rea (G14 = C, Si, Ge,...

Cited by 3 publications

References 59 publications

Reactivity of the Intramolecular Vicinal Group-13/P- and B/Group-15-Based Frustrate Lewis Pairs with Sulfur Dioxide: Mechanistic Insight from DFT

Reactivity of the Intramolecular Vicinal Group-13/P- and B/Group-15-Based Frustrate Lewis Pairs with Sulfur Dioxide: Mechanistic Insight from DFT

Investigating the Reactivity of Removing a Sulfur Atom from Propylene Sulfide with a Geminal Frustrated Lewis Pair and the Origin of Their Activation Barriers

Understanding the CO capture reaction through electronic structure analysis of four-membered-ring group-13/N- and B/group-15-based Lewis acid–base pairs

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