Predicted Gas-Phase and Liquid-Phase Acidities of Carborane Carboxylic and Dicarboxylic Acids

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

Predicted Gas-Phase and Liquid-Phase Acidities of Carborane Carboxylic and Dicarboxylic Acids

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2018

Confidentiality

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

Name of the periodical

ChemistrySelect

ISSN

2365-6549

e-ISSN

—

Volume of the periodical

3

Issue of the periodical within the volume

16

Country of publishing house

DE - GERMANY

Number of pages

10

Pages from-to

4344-4353

UT code for WoS article

000431626800031

EID of the result in the Scopus database

2-s2.0-85046079652