Electronic structures and reactivities of iodinating agents in the gas phase and in solutions: A density functional study |
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Authors: | V. D. Filimonov E. A. Krasnokutskaya O. Kh. Poleshchuk Yu. A. Lesina V. K. Chaikovskii |
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Affiliation: | (1) Tomsk Polytechnical University, 30 prosp. Lenina, 634050 Tomsk, Russian Federation;(2) Tomsk State Pedagogical University, 75 Komsomol’skii prosp., 634050 Tomsk, Russian Federation |
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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. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1280–1288, August, 2006. |
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Keywords: | halogenation reactivity iodinating agents quantum chemistry DFT B3LYP/6 311G quantum chemical method |
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