| Tartalom: |
http://real.mtak.hu/5541/ |
| Archívum: |
MTA Könyvtár |
| Gyűjtemény: |
Status = Published
Type = Article
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| Cím: |
Molecular electrostatics, energetics and dynamics of the alkylation of naphthalane: Positional isomerization of monoalkylnaphthalenes at Hartree-Fock and correlated levels with BSSE-corrections
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| Létrehozó: |
Tasi, Gyula
Mizukami, F.
Toba, M.
Niwa, S-I.
Pálinkó, István
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| Kiadó: |
Elsevier
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| Dátum: |
2000
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| Téma: |
QD Chemistry / kémia
QD02 Physical chemistry / fizikai kémia
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| Tartalmi leírás: |
The energetics and dynamics of the protonation of the naphthalene molecule were investigated at the Hartree-
Fock (HF) and correlated levels. Calculations at correlated levels reproduced the experimental gas-phase
proton affinity and basicity of naphthalene quite well. Positional isomerizations of monoalkylnaphthalenes
were studied at various theoretical levels. The calculated thermodynamic equilibrium compositions at correlated
levels are in good agreement with the experimental results. According to the calculations, intramolecular
shifts are possible for the methyl, ethyl, and isopropyl groups. By contrast, the bulky tert-butyl group transfers
exclusively intermolecularly. In accordance with the experimental results, the activation energies of the 1,2-
alkyl shifts decrease with the increase in the size of the alkyl group. This indicates that the rate-determining
step of the isomerization reactions is the rearrangement of the monoalkylnaphthalenium ions via 1,2-alkyl
shifts. An intermolecular methyl group transfer between two naphthalene molecules is energetically much
less favored than the relevant intramolecular one. However, an appropriate basis set superposition error
correction to the total energy of the three-body transition state complex is of utmost importance at secondorder
Mřller-Plesset level.
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| Típus: |
Article
PeerReviewed
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| Formátum: |
text
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| Azonosító: |
Tasi, Gyula and Mizukami, F. and Toba, M. and Niwa, S-I. and Pálinkó, István (2000) Molecular electrostatics, energetics and dynamics of the alkylation of naphthalane: Positional isomerization of monoalkylnaphthalenes at Hartree-Fock and correlated levels with BSSE-corrections. JOURNAL OF PHYSICAL CHEMISTRY A, 104 (6). pp. 1337-1345. ISSN 1089-5639
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