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2010 | 8 | 5 | 1097-1104
Tytuł artykułu

NBO and NICS analysis of the allylic rearrangements (the Cope and 3-aza-Cope rearrangements) of hexa-1,5-diene and N-vinylprop-2-en-1-amine: A DFT study

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Języki publikacji
EN
Abstrakty
EN
In this work, ab initio density functional theory (DFT) calculations have been performed on the 3,3-sigmatropic rearrangements of hexa-1,5-diene (Cope) and N-vinylprop-2-en-1-amine (3-aza-Cope) in the gas phase. The barrier heights and heats of reactions calculated at the B3LYP/6-311G** level of theory were in good agreement with experimental data. Transition states optimized with B3LYP/6-311G** theory were used for calculating the nucleus independent chemical shift (NICS) and, a natural bond orbital (NBO) analysis was also performed at the same level of theory. Our results indicate that the aromaticities of the transition states are controlled by the out-of-plane component and that the chair-like transition state of the Cope rearrangement exhibits the strongest aromatic character. Analysis of donor-acceptor (bonding and anti-bonding) interactions of σ3–4 → π*1–2 suggests that the TS structure in the hexa-1,5-diene reaction (the Cope rearrangement) has more aromatic character than the N-vinylprop-2-en-1-amine reaction (the 3-aza-Cope rearrangement). The NBO results show that in the hexa-1,5-diene and N-vinylprop-2-en-1-amine rearrangements, activation energies are controlled by σ3–4 → π*1–2 and σ3–4 → π*1–2 resonance energies. [...]
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Wydawca

Czasopismo
Rocznik
Tom
8
Numer
5
Strony
1097-1104
Opis fizyczny
Daty
wydano
2010-10-01
online
2010-09-05
Twórcy
autor
  • Chemistry Department, Islamic Azad University, Shahrood Branch P.O.box 36155/133, Shahrood, Iran
autor
  • Chemistry Department, Shahrood University of Technology, P.O.box 316, Shahrood, Iran
Bibliografia
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Typ dokumentu
Bibliografia
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Identyfikator YADDA
bwmeta1.element.-psjd-doi-10_2478_s11532-010-0084-1
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