Kwantowochemiczne studia reakcji [2+3] cykloaddycji N-tlenku formyloiminy

• Autorzy: Barański, A.

Warianty tytułu

EN

Quantum-chemical studies of parent nitrone [2+3] cycloaddition

• Języki publikacji: PL

Abstrakty

EN

The present paper is an attempt to systematize the literature data concerning quantochemical calculations of transition states for [2+3] cycloaddition of parent nitrone to alkenes, thioformaldehyde, isocyanates, acetylene and molecular oxygen. In the case of reaction with ethylene the attained transition states are nearly symmetrical. Individual methods differ in their estimation of of the resultant bonds is more advanced. For reaction in question there is a lack of experimental parameters of activation. It is generally know, however, that activation energy for [2+3] cycloaddition of typical nitrones to alkenes are in range 13-18 kcal/mol. In the case of HF calculations the activation energy is clearly overestimated. Better results are attained by taking into account the electron correlation, in which the most accurate results are obtained using the advanced method MP4SDQ. The MP2 method considerably loweres the values of activation energy, which rectifies methods MP3 and MP4. Differing results are also obtained using density functional theory (DFT). As expected the most unreliable results were obtained using VWN functional. Only calculations close to the NLDA approximation allowed the attainment of reliable results. If the MP4 method is taken as the reference method, then the closed to this as regards activation energy values is the functional B3LYP. A much lesser influence on the description of the reaction under discussion is the type of basis set. The results of the HF calculations (without electron correlation) are equaly unreliable in the minimal STO-3G base, as well as in the more advanced 6-311G** base. So for a reasonably reliable description of the reaction of [2+3] cycloaddition between nitrones and alkenes, it seems imperative to apply the methods which take into account the effects of electron correlation. A similar relationship of activation energy regarding the type of calculation method applied can be observed in the case of reaction of parent nitrone with thioformaldehyde, isocyanates, acetylene and molecular oxygen.

Słowa kluczowe

PL

reakcja [2+3] cykloaddycji

• Czasopismo: Wiadomości Chemiczne
• Rocznik: 2000
• Tom: [Z] 54, 1-2
• Strony: 53-66
• Opis fizyczny: tab., wykr., bibliogr. 30 poz.

Twórcy

autor

Barański, A.

• Instytut Chemii i Technologii Organicznej Politechniki Krakowskiej ul. Warszawska 24, 31-155 Kraków

• Instytut Chemii i Technologii Organicznej Politechniki Krakowskiej ul. Warszawska 24, 31-155 Kraków

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Uwagi

PL

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