Počet záznamů: 1  

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

  1. 1.
    SYSNO ASEP0489465
    Druh ASEPJ - Článek v odborném periodiku
    Zařazení RIVJ - Článek v odborném periodiku
    Poddruh JČlánek ve WOS
    NázevPredicted Gas-Phase and Liquid-Phase Acidities of Carborane Carboxylic and Dicarboxylic Acids
    Tvůrce(i) Oliva-Enrich, J. M. (ES)
    Humbel, S. (FR)
    Santaballa, J.A. (ES)
    Alkorta, I. (ES)
    Notario, R. (ES)
    Dávalos, J. Z. (ES)
    Canle-L., M. (ES)
    Bernhardt, E. (DE)
    Holub, Josef (UACH-T) SAI, RID, ORCID
    Hnyk, Drahomír (UACH-T) SAI, RID, ORCID
    Celkový počet autorů10
    Zdroj.dok.ChemistrySelect. - : Wiley - ISSN 2365-6549
    Roč. 3, č. 16 (2018), s. 4344-4353
    Poč.str.10 s.
    Jazyk dok.eng - angličtina
    Země vyd.DE - Německo
    Klíč. slovaAcidity ; Carboranes ; Computational Chemistry ; Delocalization Energy ; Electronic Structure
    Vědní obor RIVCA - Anorganická chemie
    Obor OECDInorganic and nuclear chemistry
    Institucionální podporaUACH-T - RVO:61388980
    UT WOS000431626800031
    EID SCOPUS85046079652
    DOI10.1002/slct.201800683
    AnotaceBy 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.
    PracovištěÚstav anorganické chemie
    KontaktJana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931
    Rok sběru2019
Počet záznamů: 1  

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