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 = -NO 2 , -CN, -CHO, -F, -H, -CH 3 , -OH, -OCH 3 , -NH 2 ; 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 (ω N) and local electrophilicity index (ω 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. © 2007 Springer-Verlag.