Abstract
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 CH2Cl2 on the X-Hal bond homolysis and heterolysis were determined using the PCM model.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1280–1288, August, 2006.
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Filimonov, V.D., Krasnokutskaya, E.A., Poleshchuk, O.K. et al. Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: A density functional study. Russ Chem Bull 55, 1328–1336 (2006). https://doi.org/10.1007/s11172-006-0422-9
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DOI: https://doi.org/10.1007/s11172-006-0422-9