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 CH 2Cl2 on the X-Hal bond homolysis and heterolysis were determined using the PCM model.
| Original language | English |
|---|---|
| Pages (from-to) | 1328-1336 |
| Number of pages | 9 |
| Journal | Russian Chemical Bulletin |
| Volume | 55 |
| Issue number | 8 |
| DOIs | |
| Publication status | Published - 1 Aug 2006 |
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Keywords
- DFT B3LYP/6 311G quantum chemical method
- Halogenation
- Iodinating agents
- Quantum chemistry
- Reactivity
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Electronic structures and reactivities of iodinating agents in the gas phase and in solutions : A density functional study. / Filimonov, V. D.; Krasnokutskaya, E. A.; Poleshchuk, O. Kh; Lesina, Yu A.; Chaikovskii, V. K.
In: Russian Chemical Bulletin, Vol. 55, No. 8, 01.08.2006, p. 1328-1336.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Electronic structures and reactivities of iodinating agents in the gas phase and in solutions
T2 - A density functional study
AU - Filimonov, V. D.
AU - Krasnokutskaya, E. A.
AU - Poleshchuk, O. Kh
AU - Lesina, Yu A.
AU - Chaikovskii, V. K.
PY - 2006/8/1
Y1 - 2006/8/1
N2 - 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.
AB - 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.
KW - DFT B3LYP/6 311G quantum chemical method
KW - Halogenation
KW - Iodinating agents
KW - Quantum chemistry
KW - Reactivity
UR - http://www.scopus.com/inward/record.url?scp=33845963192&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33845963192&partnerID=8YFLogxK
U2 - 10.1007/s11172-006-0422-9
DO - 10.1007/s11172-006-0422-9
M3 - Article
AN - SCOPUS:33845963192
VL - 55
SP - 1328
EP - 1336
JO - Russian Chemical Bulletin
JF - Russian Chemical Bulletin
SN - 1066-5285
IS - 8
ER -