Xenon Derivatives as Aerogen Bond-Donating Catalysts for Organic Transformations: A Theoretical Study on the Metaphorical “Spherical Cow in a Vacuum” Provides Insights into Noncovalent Organocatalysis

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Xenon Derivatives as Aerogen Bond-Donating Catalysts for Organic Transformations: A Theoretical Study on the Metaphorical “Spherical Cow in a Vacuum” Provides Insights into Noncovalent Organocatalysis. / Novikov, Alexander S.; Bolotin, Dmitrii S.

в: Journal of Organic Chemistry, 09.06.2022.

Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование

BibTeX

@article{e3d3fbb3fd504729a4ce77f9dc23b916,

title = "Xenon Derivatives as Aerogen Bond-Donating Catalysts for Organic Transformations: A Theoretical Study on the Metaphorical “Spherical Cow in a Vacuum” Provides Insights into Noncovalent Organocatalysis",

abstract = "Computations indicate that cationic and noncharged xenon derivatives should exhibit higher catalytic activity than their iodine-based noncovalent organocatalytic congeners. Perfluorophenyl xenonium(II) is expected to demonstrate the best balance between catalytic activity and chemical stability for use in organocatalysis. Comparing its catalytic activity with that of isoelectronic perfluoroiodobenzene indicates that the high catalytic activity of cationic noncovalent organocatalysts is predominantly attributed to the electrostatic interactions with the reaction substrates, which cause the polarization of ligated species during the reaction progress. In contrast, the electron transfer and covalent contributions to the bonding between the catalyst and substrate have negligible effects. The dominant effect of electrostatic interactions results in a strong negative correlation between the calculated Gibbs free energies of activation for the modeled reactions and the highest potentials of the σ-holes on the central atoms of the catalysts. No such correlation is observed for noncharged catalysts.",

keywords = "Органокатализ, Слабые взаимодействия, Ксенон, Иод, Механизм реакции",

author = "Novikov, {Alexander S.} and Bolotin, {Dmitrii S.}",

year = "2022",

month = jun,

day = "9",

doi = "10.1021/acs.joc.2c00680",

language = "English",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

}

RIS

TY - JOUR

T1 - Xenon Derivatives as Aerogen Bond-Donating Catalysts for Organic Transformations: A Theoretical Study on the Metaphorical “Spherical Cow in a Vacuum” Provides Insights into Noncovalent Organocatalysis

AU - Novikov, Alexander S.

AU - Bolotin, Dmitrii S.

PY - 2022/6/9

Y1 - 2022/6/9

N2 - Computations indicate that cationic and noncharged xenon derivatives should exhibit higher catalytic activity than their iodine-based noncovalent organocatalytic congeners. Perfluorophenyl xenonium(II) is expected to demonstrate the best balance between catalytic activity and chemical stability for use in organocatalysis. Comparing its catalytic activity with that of isoelectronic perfluoroiodobenzene indicates that the high catalytic activity of cationic noncovalent organocatalysts is predominantly attributed to the electrostatic interactions with the reaction substrates, which cause the polarization of ligated species during the reaction progress. In contrast, the electron transfer and covalent contributions to the bonding between the catalyst and substrate have negligible effects. The dominant effect of electrostatic interactions results in a strong negative correlation between the calculated Gibbs free energies of activation for the modeled reactions and the highest potentials of the σ-holes on the central atoms of the catalysts. No such correlation is observed for noncharged catalysts.

AB - Computations indicate that cationic and noncharged xenon derivatives should exhibit higher catalytic activity than their iodine-based noncovalent organocatalytic congeners. Perfluorophenyl xenonium(II) is expected to demonstrate the best balance between catalytic activity and chemical stability for use in organocatalysis. Comparing its catalytic activity with that of isoelectronic perfluoroiodobenzene indicates that the high catalytic activity of cationic noncovalent organocatalysts is predominantly attributed to the electrostatic interactions with the reaction substrates, which cause the polarization of ligated species during the reaction progress. In contrast, the electron transfer and covalent contributions to the bonding between the catalyst and substrate have negligible effects. The dominant effect of electrostatic interactions results in a strong negative correlation between the calculated Gibbs free energies of activation for the modeled reactions and the highest potentials of the σ-holes on the central atoms of the catalysts. No such correlation is observed for noncharged catalysts.

KW - Органокатализ

KW - Слабые взаимодействия

KW - Ксенон

KW - Иод

KW - Механизм реакции

UR - https://www.mendeley.com/catalogue/59fa3352-1e7d-3697-acb3-9120b345ad9a/

UR - http://www.scopus.com/inward/record.url?scp=85133500849&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.2c00680

DO - 10.1021/acs.joc.2c00680

M3 - Article

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

ER -

ID: 96494415