Theoretical investigation of sulfur and halogen-substituted carbocations

Paul Kiprof, Stephen R. Miller, Melissa A. Frank

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


The stabilization of sulfur, fluorine and chlorine substituted carbocations was studied using hydride exchange reactions at the G2 level of theory; evaluation of the π bonding in these was performed using variation of the dihedral angle in the case of sulfur compounds and NRT and other bond order calculations for all compounds. Resonance contributors were estimated using the NRT method. Sulfur substitution stabilizes carbocations comparable to oxygen substitution covered previously. The stability of trisubstituted carbocations is enhanced over the oxygen analogues. Halogen substitution leads to destabilization, which is more extreme for the fluorine-substituted carbocations.

Original languageEnglish (US)
Pages (from-to)61-67
Number of pages7
JournalJournal of Molecular Structure: THEOCHEM
Issue number1-3
StatePublished - May 30 2006


  • Bond order
  • Carbocation
  • Chlorine
  • Fluorine
  • G2
  • Hydride exchange
  • NBO
  • NRT
  • Resonance
  • Sulfur


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