Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: A density functional study

V. D. Filimonov, E. A. Krasnokutskaya, O. Kh Poleshchuk, Yu A. Lesina, V. K. Chaikovskii

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The electronic and spatial structures of a broad spectrum of neutral compounds with X-Hal (X = N, O, Cl; Hal = Cl, Br, I) bonds and their protonated forms and of different electronic states of triiodide cation, I3 +, were determined from density functional B3LYP/6 311G*quantum chemical calculations. The effects of the structure of these compounds on the parameters of electrophilic reactivity were revealed and the thermochemical characteristics of homolytic and heterolytic X-Hal bond dissociation and of iodine transfer in hydroxyl-containing solvents were calculated. Due to low homolytic bond dissociation energies of X-I, the formation of molecular iodine and triiodide cation I3 + becomes thermodynamically favorable and the cation should act as iodinating agent alternative to acylhypoiodites and N-iodoimides. The solvation effects of MeOH and CH 2Cl2 on the X-Hal bond homolysis and heterolysis were determined using the PCM model.

Original languageEnglish
Pages (from-to)1328-1336
Number of pages9
JournalRussian Chemical Bulletin
Issue number8
Publication statusPublished - 1 Aug 2006



  • DFT B3LYP/6 311G quantum chemical method
  • Halogenation
  • Iodinating agents
  • Quantum chemistry
  • Reactivity

ASJC Scopus subject areas

  • Chemistry(all)

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