Theoretical analysis of some substituted imine-enamine tautomerism

Patricia Pérez, Alejandro Toro-Labbé

Resultado de la investigación: Article

31 Citas (Scopus)

Resumen

We present a theoretical study of the CH3CXNH ⇌ CH2CXNH2 tautomerism. The analysis is performed in terms of global descriptors of reactivity, such as electronic chemical potential, chemical hardness and chemical softness. Chemical hardness is used to study the relative stability in the frame of the maximum hardness principle. Chemical softness appears to be related to the molecular polarizability, and it is used to discuss relative stability in the context of the minimum polarizability principle. Both empirical rules are simultaneously satisfied for this equilibrium. Transition states, in which the transferred proton is found about midway between the donor and acceptor atoms, are rationalized in terms of the Brönsted coefficient for the relative position along the reaction coordinate and the Marcus equation for the energy barriers. Substituent effects on the activation properties are analyzed in a partitioned form that probes the effect of the substituent group on the molecular properties at the ground-state and transition-state structures.

Idioma originalEnglish
Páginas (desde-hasta)422-430
Número de páginas9
PublicaciónTheoretical Chemistry Accounts
Volumen105
N.º6
DOI
EstadoPublished - may 2001

Huella dactilar

Imines
imines
softness
hardness
Hardness
molecular properties
Chemical potential
Energy barriers
Electron transitions
Ground state
Protons
reactivity
Chemical activation
activation
Atoms
ground state
protons
probes
coefficients
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

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abstract = "We present a theoretical study of the CH3CXNH ⇌ CH2CXNH2 tautomerism. The analysis is performed in terms of global descriptors of reactivity, such as electronic chemical potential, chemical hardness and chemical softness. Chemical hardness is used to study the relative stability in the frame of the maximum hardness principle. Chemical softness appears to be related to the molecular polarizability, and it is used to discuss relative stability in the context of the minimum polarizability principle. Both empirical rules are simultaneously satisfied for this equilibrium. Transition states, in which the transferred proton is found about midway between the donor and acceptor atoms, are rationalized in terms of the Br{\"o}nsted coefficient for the relative position along the reaction coordinate and the Marcus equation for the energy barriers. Substituent effects on the activation properties are analyzed in a partitioned form that probes the effect of the substituent group on the molecular properties at the ground-state and transition-state structures.",
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Theoretical analysis of some substituted imine-enamine tautomerism. / Pérez, Patricia; Toro-Labbé, Alejandro.

En: Theoretical Chemistry Accounts, Vol. 105, N.º 6, 05.2001, p. 422-430.

Resultado de la investigación: Article

TY - JOUR

T1 - Theoretical analysis of some substituted imine-enamine tautomerism

AU - Pérez, Patricia

AU - Toro-Labbé, Alejandro

PY - 2001/5

Y1 - 2001/5

N2 - We present a theoretical study of the CH3CXNH ⇌ CH2CXNH2 tautomerism. The analysis is performed in terms of global descriptors of reactivity, such as electronic chemical potential, chemical hardness and chemical softness. Chemical hardness is used to study the relative stability in the frame of the maximum hardness principle. Chemical softness appears to be related to the molecular polarizability, and it is used to discuss relative stability in the context of the minimum polarizability principle. Both empirical rules are simultaneously satisfied for this equilibrium. Transition states, in which the transferred proton is found about midway between the donor and acceptor atoms, are rationalized in terms of the Brönsted coefficient for the relative position along the reaction coordinate and the Marcus equation for the energy barriers. Substituent effects on the activation properties are analyzed in a partitioned form that probes the effect of the substituent group on the molecular properties at the ground-state and transition-state structures.

AB - We present a theoretical study of the CH3CXNH ⇌ CH2CXNH2 tautomerism. The analysis is performed in terms of global descriptors of reactivity, such as electronic chemical potential, chemical hardness and chemical softness. Chemical hardness is used to study the relative stability in the frame of the maximum hardness principle. Chemical softness appears to be related to the molecular polarizability, and it is used to discuss relative stability in the context of the minimum polarizability principle. Both empirical rules are simultaneously satisfied for this equilibrium. Transition states, in which the transferred proton is found about midway between the donor and acceptor atoms, are rationalized in terms of the Brönsted coefficient for the relative position along the reaction coordinate and the Marcus equation for the energy barriers. Substituent effects on the activation properties are analyzed in a partitioned form that probes the effect of the substituent group on the molecular properties at the ground-state and transition-state structures.

KW - Hardness profile

KW - Imine-enamine tautomerism

KW - Polarizability profile

KW - Proton transfer

KW - Transition state

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DO - 10.1007/s002140000223

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