Affordable Access

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

Publication Date
  • Philicity
  • Electrophilicity
  • Spin Polarized Density Functional Theory
  • Triplet Carbenes
  • Singlet Carbenes
  • Chemical Reactivity
  • Local Electrophilicity Descriptors
  • Generalized Philicity Concept
  • Singlet-Triplet Gaps
  • Cyclopropanation Reactions
  • Intermolecular Reactivity
  • Cycloaddition Reactions
  • 2-State Reactivity
  • Transition-States
  • Cyclo-Additions
  • Small Molecules
  • Chemistry


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.

There are no comments yet on this publication. Be the first to share your thoughts.


Seen <100 times