Predicted Gas-Phase and Liquid-Phase Acidities of Carborane Carboxylic and Dicarboxylic Acids
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F18%3A00489465" target="_blank" >RIV/61388980:_____/18:00489465 - isvavai.cz</a>
Výsledek na webu
<a href="http://dx.doi.org/10.1002/slct.201800683" target="_blank" >http://dx.doi.org/10.1002/slct.201800683</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/slct.201800683" target="_blank" >10.1002/slct.201800683</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Predicted Gas-Phase and Liquid-Phase Acidities of Carborane Carboxylic and Dicarboxylic Acids
Popis výsledku v původním jazyce
By means of MP2 and DFT computations we predict gas-phase acidities and liquid-phase (MeCN) acidities of (di)carboxylic acids derived from icosahedral ortho, meta, and para-carboranes. For comparative purpose, we include the benzoic and phthalic acids. Substitution of benzene by a carborane cage – cage effect – strikingly increases the gas-phase acidity (lower GA) for the (di)carboxylic acids, being the ortho isomers always the most acidic, following the order ortho ≫ meta > para. The computed GA of the dicarboxylic acid derived from ortho-carborane is far lower than sulphuric acid, due to an enhanced stabilization of the carboxylate through an intramolecular OHO bridge connection, also taking place in phthalic acid. The change of GA relative to ortho, meta and para positions of the carboxylic groups isomer effect is larger for carboranes. As regards to liquid-phase (MeCN), the computations show that carborane (di)carboxylic acids also show a larger acidity (lower pK a ) as compared to the phthalic acids and that the dicarboxylic ortho-carborane is also a superacid in the liquid phase (MeCN), due to the OHO bridge connection in the carboxylate, as in the gas phase. Additional computations show how much of this isomeric effect is to be attributed to the electronic delocalization.
Název v anglickém jazyce
Predicted Gas-Phase and Liquid-Phase Acidities of Carborane Carboxylic and Dicarboxylic Acids
Popis výsledku anglicky
By means of MP2 and DFT computations we predict gas-phase acidities and liquid-phase (MeCN) acidities of (di)carboxylic acids derived from icosahedral ortho, meta, and para-carboranes. For comparative purpose, we include the benzoic and phthalic acids. Substitution of benzene by a carborane cage – cage effect – strikingly increases the gas-phase acidity (lower GA) for the (di)carboxylic acids, being the ortho isomers always the most acidic, following the order ortho ≫ meta > para. The computed GA of the dicarboxylic acid derived from ortho-carborane is far lower than sulphuric acid, due to an enhanced stabilization of the carboxylate through an intramolecular OHO bridge connection, also taking place in phthalic acid. The change of GA relative to ortho, meta and para positions of the carboxylic groups isomer effect is larger for carboranes. As regards to liquid-phase (MeCN), the computations show that carborane (di)carboxylic acids also show a larger acidity (lower pK a ) as compared to the phthalic acids and that the dicarboxylic ortho-carborane is also a superacid in the liquid phase (MeCN), due to the OHO bridge connection in the carboxylate, as in the gas phase. Additional computations show how much of this isomeric effect is to be attributed to the electronic delocalization.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10402 - Inorganic and nuclear chemistry
Návaznosti výsledku
Projekt
—
Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2018
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
ChemistrySelect
ISSN
2365-6549
e-ISSN
—
Svazek periodika
3
Číslo periodika v rámci svazku
16
Stát vydavatele periodika
DE - Spolková republika Německo
Počet stran výsledku
10
Strana od-do
4344-4353
Kód UT WoS článku
000431626800031
EID výsledku v databázi Scopus
2-s2.0-85046079652