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

Open/ Download
Publication date
2007Metadata
Show full item record
Cómo citar
Guerra, Doris
Cómo citar
Understanding the chemical reactivity of phenylhalocarbene systems: an analysis based on the spin-polarized density functional theory
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 (omega(N)) and local electrophilicity index (omega(N,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.
General note
Artículo de publicación ISI
Identifier
URI: https://repositorio.uchile.cl/handle/2250/118685
Quote Item
THEORETICAL CHEMISTRY ACCOUNTS Vol. 118 AUG 2007 2 325-335
Collections