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

Research output: Contribution to journalArticle

15 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)325-335
Number of pages11
JournalTheoretical Chemistry Accounts
Volume118
Issue number2
DOIs
Publication statusPublished - 1 Aug 2007

Keywords

  • Chemical reactivity
  • Electrophilicity
  • Philicity
  • Singlet carbenes
  • Spin polarized density functional theory
  • Triplet carbenes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Understanding the chemical reactivity of phenylhalocarbene systems: An analysis based on the spin-polarized density functional theory'. Together they form a unique fingerprint.

  • Cite this