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

Bibliographic Details
Parent link:Russian Chemical Bulletin.— , 1952
Vol. 55, № 8.— 2006.— P. 1328-1336
Other Authors: Filimonov V. D. Viktor Dmitrievich, Krasnokutskaya E. A., Poleshuk O. K., Lesina Y. Y., Chaikovskii V. K. Vitold Kazimirovich
Summary: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.
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Language:English
Published: 2006
Subjects:
Format: Book Chapter
KOHA link:https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=596136