Počet záznamů: 1
Predicted Gas-Phase and Liquid-Phase Acidities of Carborane Carboxylic and Dicarboxylic Acids
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SYSNO ASEP 0489465 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Predicted 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, ORCIDCelkový počet autorů 10 Zdroj.dok. ChemistrySelect. - : Wiley - ISSN 2365-6549
Roč. 3, č. 16 (2018), s. 4344-4353Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. DE - Německo Klíč. slova Acidity ; Carboranes ; Computational Chemistry ; Delocalization Energy ; Electronic Structure Vědní obor RIV CA - Anorganická chemie Obor OECD Inorganic and nuclear chemistry Institucionální podpora UACH-T - RVO:61388980 UT WOS 000431626800031 EID SCOPUS 85046079652 DOI 10.1002/slct.201800683 Anotace 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. Pracoviště Ústav anorganické chemie Kontakt Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Rok sběru 2019
Počet záznamů: 1