Understanding the chemical reactivity of phenylhalocarbene systems: An analysis based on the spin-polarized density functional theory

Doris Guerra, Juan Andrés, Eduardo Chamorro, Patricia Pérez

Resultado de la investigación: Article

15 Citas (Scopus)

Resumen

Global and local indices based on the spin-polarized density functional theory (SP-DFT) have been used to rationalize the philicity power and spin polarization pattern of a family of singlet substituted phenylhalocarbenes, (pYPhXC, Y = -NO2 , -CN, -CHO, -F, -H, -CH3 , -OH, -OCH3 , -NH2 ; X = -F, -Cl, -Br). The local reactivity may be traced out by the simple condensed-to-atoms model for the SP-DFT Fukui functions, namely f+NS,k and f+SS,k. For the addition of some singlet phenylhalocarbenes on tetramethylethylene a linear correlation among the global (ωN) and local electrophilicity index (ωN,C), and the observed rate constants were found. This result supports a mechanistic model where the carbene adds to the olefin in a single step that is controlled by the carbene electrophilicity. These results emphasize the usefulness of general SP-DFT philicities in the rationalization of chemical reactivity at initial stages of reactions that could involve both charge transfer and spin polarization processes.

Idioma originalEnglish
Páginas (desde-hasta)325-335
Número de páginas11
PublicaciónTheoretical Chemistry Accounts
Volumen118
N.º2
DOI
EstadoPublished - 1 ago 2007

Huella dactilar

Chemical reactivity
systems analysis
Density functional theory
Spin polarization
reactivity
density functional theory
carbenes
Alkenes
Charge transfer
Rate constants
polarization
Atoms
alkenes
charge transfer
carbene
atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

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abstract = "Global and local indices based on the spin-polarized density functional theory (SP-DFT) have been used to rationalize the philicity power and spin polarization pattern of a family of singlet substituted phenylhalocarbenes, (pYPhXC, Y = -NO2 , -CN, -CHO, -F, -H, -CH3 , -OH, -OCH3 , -NH2 ; X = -F, -Cl, -Br). The local reactivity may be traced out by the simple condensed-to-atoms model for the SP-DFT Fukui functions, namely f+NS,k and f+SS,k. For the addition of some singlet phenylhalocarbenes on tetramethylethylene a linear correlation among the global (ωN) and local electrophilicity index (ωN,C), and the observed rate constants were found. This result supports a mechanistic model where the carbene adds to the olefin in a single step that is controlled by the carbene electrophilicity. These results emphasize the usefulness of general SP-DFT philicities in the rationalization of chemical reactivity at initial stages of reactions that could involve both charge transfer and spin polarization processes.",
keywords = "Chemical reactivity, Electrophilicity, Philicity, Singlet carbenes, Spin polarized density functional theory, Triplet carbenes",
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TY - JOUR

T1 - Understanding the chemical reactivity of phenylhalocarbene systems

T2 - An analysis based on the spin-polarized density functional theory

AU - Guerra, Doris

AU - Andrés, Juan

AU - Chamorro, Eduardo

AU - Pérez, Patricia

PY - 2007/8/1

Y1 - 2007/8/1

N2 - Global and local indices based on the spin-polarized density functional theory (SP-DFT) have been used to rationalize the philicity power and spin polarization pattern of a family of singlet substituted phenylhalocarbenes, (pYPhXC, Y = -NO2 , -CN, -CHO, -F, -H, -CH3 , -OH, -OCH3 , -NH2 ; X = -F, -Cl, -Br). The local reactivity may be traced out by the simple condensed-to-atoms model for the SP-DFT Fukui functions, namely f+NS,k and f+SS,k. For the addition of some singlet phenylhalocarbenes on tetramethylethylene a linear correlation among the global (ωN) and local electrophilicity index (ωN,C), and the observed rate constants were found. This result supports a mechanistic model where the carbene adds to the olefin in a single step that is controlled by the carbene electrophilicity. These results emphasize the usefulness of general SP-DFT philicities in the rationalization of chemical reactivity at initial stages of reactions that could involve both charge transfer and spin polarization processes.

AB - Global and local indices based on the spin-polarized density functional theory (SP-DFT) have been used to rationalize the philicity power and spin polarization pattern of a family of singlet substituted phenylhalocarbenes, (pYPhXC, Y = -NO2 , -CN, -CHO, -F, -H, -CH3 , -OH, -OCH3 , -NH2 ; X = -F, -Cl, -Br). The local reactivity may be traced out by the simple condensed-to-atoms model for the SP-DFT Fukui functions, namely f+NS,k and f+SS,k. For the addition of some singlet phenylhalocarbenes on tetramethylethylene a linear correlation among the global (ωN) and local electrophilicity index (ωN,C), and the observed rate constants were found. This result supports a mechanistic model where the carbene adds to the olefin in a single step that is controlled by the carbene electrophilicity. These results emphasize the usefulness of general SP-DFT philicities in the rationalization of chemical reactivity at initial stages of reactions that could involve both charge transfer and spin polarization processes.

KW - Chemical reactivity

KW - Electrophilicity

KW - Philicity

KW - Singlet carbenes

KW - Spin polarized density functional theory

KW - Triplet carbenes

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