Exploring borderline S<sub>N</sub>1–S<sub>N</sub>2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride

de Andrade, Karine Nascimento; Peixoto, Bárbara Pereira; Carneiro, José Walkimar de Mesquita; Fiorot, Rodolfo Goetze

doi:10.1039/d4ra00066h

RSC Adv.

2024

DOI: 10.1039/d4ra00066h

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Exploring borderline S_N1–S_N2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride

Karine Nascimento de Andrade,

Bárbara Pereira Peixoto,

José Walkimar de Mesquita Carneiro

et al.

Abstract: We explored borderline SNX reactions quantum-chemically, revealing a preferred dissociative-SN2 pathway controlled by solute–solvent interactions through various solvation models.

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Zeolites as Solid Solvents: Explaining the Chloromethane Hydrolysis over Metal-Exchanged Zeolite Y by DFT Calculations

Rosenbach,

Fernandes,

Mota

2024

ACS Omega

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We report a theoretical DFT study of the reaction pathways for chloromethane hydrolysis over metal-exchanged zeolites (Li + , Na + , K + , and Mg 2+ ). A cluster of 78 T atoms (T referring to Si or Al atoms), comprising the zeolite Y super cavity coupled with the sodalite cage and three hexagonal prism units (Si (78−x) Al x O 129 H 54 ; x = 1 or 2), was used in the calculations. The study was carried out using the ONIOM method. The high layer was computed at M062X/6-31+ +G(d,p), whereas the low layer was computed at the PM6 level of theory. The energy profile was obtained by single-point calculations at the M062X/6-31++G(d,p) for the entire structure. The first step studied was the adsorption of chloromethane on the zeolite, which involves an ion−dipole interaction between the metal cation and the chlorine atom. Then, two mechanistic pathways were investigated: one via formation of an adsorbed methoxide and the other involving a direct, one-step, nucleophilic attack of the water molecule to the adsorbed chloromethane. In all systems studied, the direct mechanism showed a lower energy of activation than the route involving the methoxide intermediate. The same behavior was also observed for chloromethane methanolysis to afford dimethyl ether on the metal-exchanged zeolites. The theoretical results are in agreement with the experiments of chloromethane hydrolysis over metal-exchanged zeolite Y, explaining the formation of dimethyl ether upon chloromethane methanolysis on zeolites of low or no acidity. The transition state for the direct route resembles a S N 2 process assisted by the surface, reinforcing the concept of zeolites as solid solvents, providing a polar nanoenvironment that favors and assists the formation of ionic transition states and intermediates.

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Zeolites as Solid Solvents: Explaining the Chloromethane Hydrolysis over Metal-Exchanged Zeolite Y by DFT Calculations

Rosenbach,

Fernandes,

Mota

2024

ACS Omega

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Exploring borderline S_N1–S_N2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride

Abstract: We explored borderline SNX reactions quantum-chemically, revealing a preferred dissociative-SN2 pathway controlled by solute–solvent interactions through various solvation models.

Cited by 1 publication

References 63 publications

Zeolites as Solid Solvents: Explaining the Chloromethane Hydrolysis over Metal-Exchanged Zeolite Y by DFT Calculations

Zeolites as Solid Solvents: Explaining the Chloromethane Hydrolysis over Metal-Exchanged Zeolite Y by DFT Calculations

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Exploring borderline SN1–SN2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride

Abstract: We explored borderline SNX reactions quantum-chemically, revealing a preferred dissociative-SN2 pathway controlled by solute–solvent interactions through various solvation models.

Cited by 1 publication

References 63 publications

Zeolites as Solid Solvents: Explaining the Chloromethane Hydrolysis over Metal-Exchanged Zeolite Y by DFT Calculations

Zeolites as Solid Solvents: Explaining the Chloromethane Hydrolysis over Metal-Exchanged Zeolite Y by DFT Calculations

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Exploring borderline S_N1–S_N2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride