Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory

The density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM) have been used to study the lowest lying spin states of the photochemical hydrogen abstraction reaction by formaldehyde, acetaldehyde, and acetone in the presence of different hydrogen donors: propane, 2-propanol, a...

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Principais autores: Firme, Caio Lima, Garden, Simon John, Lucas, Nanci Câmara de, Nicodem, David Ernest, Corrêa, Rodrigo José
Formato: article
Idioma:English
Publicado em: American Chemical Society
Assuntos:
Hydrogen abstraction
Carbonyls
Oxygen
Hydrogen
Chemical reactions
Endereço do item:https://repositorio.ufrn.br/jspui/handle/123456789/29212
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spelling ri-123456789-292122021-02-15T19:10:45Z Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory Firme, Caio Lima Garden, Simon John Lucas, Nanci Câmara de Nicodem, David Ernest Corrêa, Rodrigo José Hydrogen abstraction Carbonyls Oxygen Hydrogen Chemical reactions The density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM) have been used to study the lowest lying spin states of the photochemical hydrogen abstraction reaction by formaldehyde, acetaldehyde, and acetone in the presence of different hydrogen donors: propane, 2-propanol, and methylamine. Calculations of all the critical points on the PES of these reactions were performed at uB3LYP/6-311++G(d,p). Methylamine is the best hydrogen donor, in thermodynamic and kinetic terms, followed by 2-propanol and finally propane. Secondary C–H hydrogen abstraction in 2-propanol and C–H abstraction in methylamine is thermodynamically and kinetically favored with respect to hydrogen abstraction from the OH and NH functional groups. Charge transfer takes place before the transition state when methylamine is the hydrogen donor, and for other hydrogen donors, charge transfer begins only in the transition state. The extent of the charge transfer in the transition states corresponds to about 50% of the total change in electron density of the oxygen atom of the T1 carbonyl compounds during the course of the hydrogen abstraction reactions. The effect of solvent was investigated using the continuum solvation model for the reaction of triplet acetaldehyde in acetonitrile, which resulted in a barrierless transition state for hydrogen abstraction from methylamine. 2020-06-10T03:35:22Z 2020-06-10T03:35:22Z 2012-12-18 article FIRME, Caio Lima; GARDEN, Simon John; LUCAS, Nanci Câmara de; NICODEM, David Ernest; CORRÊA, Rodrigo José. Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory. The Journal Of Physical Chemistry A, [s. l.], v. 117, n. 2, p. 439-450, 18 dez. 2012. ISSN 1520-5215 versão online. DOI https://doi.org/10.1021/jp307505e. Disponível em: https://pubs.acs.org/doi/10.1021/jp307505e. Acesso em: 09 jun. 2020. 1520-5215 https://repositorio.ufrn.br/jspui/handle/123456789/29212 10.1021/jp307505e en Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ application/pdf American Chemical Society
institution Repositório Institucional
collection RI - UFRN
language English
topic Hydrogen abstraction
Carbonyls
Oxygen
Hydrogen
Chemical reactions
spellingShingle Hydrogen abstraction
Carbonyls
Oxygen
Hydrogen
Chemical reactions
Firme, Caio Lima
Garden, Simon John
Lucas, Nanci Câmara de
Nicodem, David Ernest
Corrêa, Rodrigo José
Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory
description The density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM) have been used to study the lowest lying spin states of the photochemical hydrogen abstraction reaction by formaldehyde, acetaldehyde, and acetone in the presence of different hydrogen donors: propane, 2-propanol, and methylamine. Calculations of all the critical points on the PES of these reactions were performed at uB3LYP/6-311++G(d,p). Methylamine is the best hydrogen donor, in thermodynamic and kinetic terms, followed by 2-propanol and finally propane. Secondary C–H hydrogen abstraction in 2-propanol and C–H abstraction in methylamine is thermodynamically and kinetically favored with respect to hydrogen abstraction from the OH and NH functional groups. Charge transfer takes place before the transition state when methylamine is the hydrogen donor, and for other hydrogen donors, charge transfer begins only in the transition state. The extent of the charge transfer in the transition states corresponds to about 50% of the total change in electron density of the oxygen atom of the T1 carbonyl compounds during the course of the hydrogen abstraction reactions. The effect of solvent was investigated using the continuum solvation model for the reaction of triplet acetaldehyde in acetonitrile, which resulted in a barrierless transition state for hydrogen abstraction from methylamine.
format article
author Firme, Caio Lima
Garden, Simon John
Lucas, Nanci Câmara de
Nicodem, David Ernest
Corrêa, Rodrigo José
author_facet Firme, Caio Lima
Garden, Simon John
Lucas, Nanci Câmara de
Nicodem, David Ernest
Corrêa, Rodrigo José
author_sort Firme, Caio Lima
title Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory
title_short Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory
title_full Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory
title_fullStr Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory
title_full_unstemmed Theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory
title_sort theoretical study of photochemical hydrogen abstraction by triplet aliphatic carbonyls by using density functional theory
publisher American Chemical Society
publishDate 2020
url https://repositorio.ufrn.br/jspui/handle/123456789/29212
work_keys_str_mv AT firmecaiolima theoreticalstudyofphotochemicalhydrogenabstractionbytripletaliphaticcarbonylsbyusingdensityfunctionaltheory
AT gardensimonjohn theoreticalstudyofphotochemicalhydrogenabstractionbytripletaliphaticcarbonylsbyusingdensityfunctionaltheory
AT lucasnancicamarade theoreticalstudyofphotochemicalhydrogenabstractionbytripletaliphaticcarbonylsbyusingdensityfunctionaltheory
AT nicodemdavidernest theoreticalstudyofphotochemicalhydrogenabstractionbytripletaliphaticcarbonylsbyusingdensityfunctionaltheory
AT correarodrigojose theoreticalstudyofphotochemicalhydrogenabstractionbytripletaliphaticcarbonylsbyusingdensityfunctionaltheory
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