Benchmark ab initio characterization of the complex potential energy surfaces of the HOO− + CH3Y [Y = F, Cl, Br, I] reactions

Tasi, Domonkos A.; Czakó, Gábor

doi:10.1039/d4cp01071j

Phys. Chem. Chem. Phys.

2024

DOI: 10.1039/d4cp01071j

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Benchmark ab initio characterization of the complex potential energy surfaces of the HOO⁻ + CH₃Y [Y = F, Cl, Br, I] reactions

Domonkos A. Tasi,

Gábor Czakó

Abstract: The α-effect is a well-known phenomenon in organic chemistry, which relates to the enhanced reactivity of nucleophiles involving one or more lone-pair electrons adjacent to the nucleophilic center. The gas-phase...

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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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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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Benchmark ab initio characterization of the complex potential energy surfaces of the HOO⁻ + CH₃Y [Y = F, Cl, Br, I] reactions

Abstract: The α-effect is a well-known phenomenon in organic chemistry, which relates to the enhanced reactivity of nucleophiles involving one or more lone-pair electrons adjacent to the nucleophilic center. The gas-phase...

Cited by 1 publication

References 119 publications

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

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

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Benchmark ab initio characterization of the complex potential energy surfaces of the HOO− + CH3Y [Y = F, Cl, Br, I] reactions

Abstract: The α-effect is a well-known phenomenon in organic chemistry, which relates to the enhanced reactivity of nucleophiles involving one or more lone-pair electrons adjacent to the nucleophilic center. The gas-phase...

Cited by 1 publication

References 119 publications

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

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

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Benchmark ab initio characterization of the complex potential energy surfaces of the HOO⁻ + CH₃Y [Y = F, Cl, Br, I] reactions

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

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