Interaction of Polar Group with a Bulky Hydrocarbon Residue : Polarizability and Steric Effects

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F05%3A00013518" target="_blank" >RIV/60461373:22310/05:00013518 - 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

Interaction of Polar Group with a Bulky Hydrocarbon Residue : Polarizability and Steric Effects

Popis výsledku v původním jazyce

Energies of two series of branched hydrocarbon monosubstituted derivatives, 2-substituted 2-methylpropanes and 1-substituted bicyclo[2.2.2]octanes with 19 different substituents were calculated at the B3LYP/6-311+G(d,p) level and compared with the energies of straight-chain 1-substituted butanes. The comparison was carried out in terms of isodesmic homodesmotic reactions, in which the substituent is transferred from one hydrocarbon residue to another. The branched derivatives are mostly stabilized, in the extreme case by as much as 30 kJ mol-1 confirming that the additive rule used for estimating the enthalpies of formation is not valid for branched derivatives. The stabilization energies DE for the individual substituents X are not proportional to anyknown substituent parameters. In the qualitative respect, they are controlled by the first atom of the substituent - similarly as in the straight-chain isomers - but in the case of sterically demanding substituents they are perturbed by

Název v anglickém jazyce

Interaction of Polar Group with a Bulky Hydrocarbon Residue : Polarizability and Steric Effects

Popis výsledku anglicky

Energies of two series of branched hydrocarbon monosubstituted derivatives, 2-substituted 2-methylpropanes and 1-substituted bicyclo[2.2.2]octanes with 19 different substituents were calculated at the B3LYP/6-311+G(d,p) level and compared with the energies of straight-chain 1-substituted butanes. The comparison was carried out in terms of isodesmic homodesmotic reactions, in which the substituent is transferred from one hydrocarbon residue to another. The branched derivatives are mostly stabilized, in the extreme case by as much as 30 kJ mol-1 confirming that the additive rule used for estimating the enthalpies of formation is not valid for branched derivatives. The stabilization energies DE for the individual substituents X are not proportional to anyknown substituent parameters. In the qualitative respect, they are controlled by the first atom of the substituent - similarly as in the straight-chain isomers - but in the case of sterically demanding substituents they are perturbed by

Druh

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

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

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Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2005

Kód důvěrnosti údajů

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

Název periodika

Collection of Czechoslovak Chemical Communications

ISSN

0010-0765

e-ISSN

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Svazek periodika

70

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

CZ - Česká republika

Počet stran výsledku

13

Strana od-do

370-382

Kód UT WoS článku

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EID výsledku v databázi Scopus

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