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: Contribución a una revistaArtículo

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

Áreas temáticas de ASJC Scopus

  • Química física y teórica

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