The influence of fluorination on the dynamics of the F− + CH3CH2I reaction

Gstir, Thomas; Michaelsen, Tim; Long, Bryan A.; Nacsa, András B.; Ayasli, Atilay; Swaraj, Dasarath; Zappa, Fábio; Trummer, Florian; Ard, Shaun G.; Shuman, Nicholas S.; Czakó, Gábor; Viggiano, A. A.; Wester, Roland

doi:10.1039/d3cp02110f

Phys. Chem. Chem. Phys.

2023

DOI: 10.1039/d3cp02110f

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The influence of fluorination on the dynamics of the F⁻ + CH₃CH₂I reaction

Thomas Gstir¹,

Tim Michaelsen²,

Bryan A. Long³

et al.

Abstract: The competition between the bimolecular nucleophilic substitution (SN2) and base-induced elimination (E2) reaction and their intrinsic reactivity is of key interest in organic chemistry. To investigate the effect of suppressing...

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2024

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Cited by 6 publications

References 48 publications

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The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO^– (X = F, *Cl, Br, I) and CH₃CH₂Cl

Fu,

Zhen,

Wang

et al. 2024

J. Phys. Chem. A

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Precise prediction of reactivity and accurately identifying the types of reaction complexes are prerequisites for delineating the microscopic mechanisms of ion−molecule reactions, which remain unclear for reactions involving α-nucleophilic reagents. Here, we investigate the potential energy surface of the multiatomic reactions XO − (X = F, *Cl, Br, I) + CH 3 CH 2 Cl to elucidate the optimal descriptors for reaction reactivity and the origin of halogen bond/hydrogen bond compounds. Through analyzing the orbital composition and the relationship of energy barriers with the proton affinity and nucleophilic index, the local nucleophilic index is ultimately determined to be the optimal descriptor for predicting the reactivity of the reactions with αnucleophilic reagents. Furthermore, it is found that the type of a reaction complex is closely related to the initial relative orientations of ions and molecules, the functional group substitutions, and the electrostatic potential extreme points of the halogen tops in the reactive substrates. In terms of the above factors, we can design suitable reaction substrates to generate intermolecular interactions with specific types, which is important in areas such as drug synthesis.

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The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO^– (X = F, *Cl, Br, I) and CH₃CH₂Cl

Fu,

Zhen,

Wang

et al. 2024

J. Phys. Chem. A

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Benchmark Ab Initio Mapping of the F^– + CH₂ClI S_N2 and Proton-Abstraction Reactions

Tasi,

Orján,

Czakó

2024

J. Phys. Chem. A

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The experimental and theoretical studies of gasphase S N 2 reactions have significantly broadened our understanding of the mechanisms governing even the simplest chemical processes. These investigations have not only advanced our knowledge of reaction pathways but also provided critical insights into the fundamental dynamics of chemical systems. Nevertheless, in the case of the prototypical X − + CH 3 Y → Y − + CH 3 X [X, Y = F, Cl, Br, and I] S N 2 reactions, the effect of the additional halogenation of CH 3 Y has not been thoroughly explored. Thus, here, we perform the first high-level ab initio characterization of the F − + CH 2 ClI S N 2 and proton-abstraction reactions utilizing the explicitly-correlated CCSD(T)-F12b method. Two possible S N 2 channels leading to the Cl − + CH 2 FI and I − + CH 2 FCl products are distinguished, in which we investigate four different pathways of back-side attack Walden inversion, front-side attack, double inversion, and halogen-bonded complex formation. In order to obtain the benchmark energies of the geometries of the stationary points, determined at the CCSD(T)-F12b/aug-cc-pVTZ level of theory, additional computations are carried out considering the basis set effects, post-CCSD(T) correlations, and core corrections. Using the benchmark data, we assess the accuracy of the MP2, DF-MP2, MP2-F12, and DF-MP2-F12 methods as well. By comparing the present F − + CH 2 ClI system with the corresponding F − + CH 3 Y [Y = Cl and I] reactions, this study demonstrates that further halogenation of CH 3 Y significantly promotes the corresponding proton-abstraction and S N 2 retention channels as well as the halogen-bonded complex formation, and as a consequence, the traditional back-side attack Walden-inversion mechanism becomes less pronounced.

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High-level analytical potential-energy-surface-based dynamics of the OH⁻ + CH₃CH₂Cl S_N2 and E2 reactions in full (24) dimensions

Nacsa,

Tokaji,

Czakó

2024

Faraday Discuss.

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The influence of fluorination on the dynamics of the F⁻ + CH₃CH₂I reaction

Abstract: The competition between the bimolecular nucleophilic substitution (SN2) and base-induced elimination (E2) reaction and their intrinsic reactivity is of key interest in organic chemistry. To investigate the effect of suppressing...

Cited by 6 publications

References 48 publications

The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO^– (X = F, *Cl, Br, I) and CH₃CH₂Cl

The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO^– (X = F, *Cl, Br, I) and CH₃CH₂Cl

Benchmark Ab Initio Mapping of the F^– + CH₂ClI S_N2 and Proton-Abstraction Reactions

High-level analytical potential-energy-surface-based dynamics of the OH⁻ + CH₃CH₂Cl S_N2 and E2 reactions in full (24) dimensions

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The influence of fluorination on the dynamics of the F− + CH3CH2I reaction

Abstract: The competition between the bimolecular nucleophilic substitution (SN2) and base-induced elimination (E2) reaction and their intrinsic reactivity is of key interest in organic chemistry. To investigate the effect of suppressing...

Cited by 6 publications

References 48 publications

The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO– (X = F, *Cl, Br, I) and CH3CH2Cl

The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO– (X = F, *Cl, Br, I) and CH3CH2Cl

Benchmark Ab Initio Mapping of the F– + CH2ClI SN2 and Proton-Abstraction Reactions

High-level analytical potential-energy-surface-based dynamics of the OH− + CH3CH2Cl SN2 and E2 reactions in full (24) dimensions

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Product

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The influence of fluorination on the dynamics of the F⁻ + CH₃CH₂I reaction

The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO^– (X = F, *Cl, Br, I) and CH₃CH₂Cl

The Investigation on the Reactivity and the Formation of Halogen Bond Complexes for the Reactions of α-Nucleophiles XO^– (X = F, *Cl, Br, I) and CH₃CH₂Cl

Benchmark Ab Initio Mapping of the F^– + CH₂ClI S_N2 and Proton-Abstraction Reactions

High-level analytical potential-energy-surface-based dynamics of the OH⁻ + CH₃CH₂Cl S_N2 and E2 reactions in full (24) dimensions