Oxidace Alkenu Manganistanem. Efekt substituentu a rozpoustedla. Problemy s MP2 vypocty

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F06%3A00049165" target="_blank" >RIV/61388955:_____/06:00049165 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Permanganate oxidation of alkenes. Substituent and solvent effects. Difficulties with MP2 calculations

Popis výsledku v původním jazyce

The permanganate oxidation of alkenes has been studied both experimentally and computationally. Transition state structures were located for the reaction of permanganate ion with a variety of monosubstituted alkenes at the B3LYP/6-311++G** level. Although the calculated activation energy for the reaction with ethene was reasonable, the calculated effect of substituents, based on the energies of the reactants, was much larger than that experimentally found. This was shown to be due to the formation of anintermediate charge-dipole complex which led to the transition state. Reaction field calculations found the complex to disappear in a high dielectric constant medium, and the range of activation energies for the reaction in solution became quite small.MP2 calculations were carried out in order to have a comparison with the DFT results. MP2-MP4 gave unusual results for calculations on permanganate ion as well as chromate ion and iron tetraoxide. ...

Název v anglickém jazyce

Permanganate oxidation of alkenes. Substituent and solvent effects. Difficulties with MP2 calculations

Popis výsledku anglicky

The permanganate oxidation of alkenes has been studied both experimentally and computationally. Transition state structures were located for the reaction of permanganate ion with a variety of monosubstituted alkenes at the B3LYP/6-311++G** level. Although the calculated activation energy for the reaction with ethene was reasonable, the calculated effect of substituents, based on the energies of the reactants, was much larger than that experimentally found. This was shown to be due to the formation of anintermediate charge-dipole complex which led to the transition state. Reaction field calculations found the complex to disappear in a high dielectric constant medium, and the range of activation energies for the reaction in solution became quite small.MP2 calculations were carried out in order to have a comparison with the DFT results. MP2-MP4 gave unusual results for calculations on permanganate ion as well as chromate ion and iron tetraoxide. ...

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2006

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

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Svazek periodika

128

Číslo periodika v rámci svazku

35

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

11537-11544

Kód UT WoS článku

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EID výsledku v databázi Scopus

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