Solvent Effects on the Monomer/Hydrogen-Bonded Dimer Equilibrium in Carboxylic Acids: (+)-(S)-Ketopinic Acid as a Case Study
| Autor: | Manuel Montejo Gámez, Pilar Gema Rodríguez Ortega, Juan Jesús López González, Fernando Márquez López |
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| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Hydrogen 010405 organic chemistry Hydrogen bond Dimer Carboxylic acid Organic Chemistry chemistry.chemical_element General Chemistry 010402 general chemistry Photochemistry 01 natural sciences Biochemistry 0104 chemical sciences Chemistry chemistry.chemical_compound Monomer chemistry Vibrational circular dichroism Physical chemistry Solvent effects Equilibrium constant |
| Zdroj: | Chemistry: an Asian journal |
| ISSN: | 1861-4728 |
| DOI: | 10.1002/asia.201600199 |
| Popis: | The hydrogen-bond-assisted self-association process of a chiral semirigid carboxylic acid, namely, (+)-(S)-ketopinic acid, has been studied. The multiconformational monomer/dimer equilibrium has been evaluated by means of a concentration-dependent FTIR study that enabled the experimental equilibrium constants of the dimer formation reaction (K-dim) to be determined in two solvents of different polarity. In CDCl3, dimeric forms predominate, even in diluted solutions (K-dim(CF) =5.074), whereas in CD3CN the self-association process is hindered and monomers are always the main species, irrespective of solute concentration (K-dim(AN) = 0.194). The reliability of the dimerization constants and the derived mono- and dimeric experimental fractions have been proven by means of accurate matching between the experimental vibrational circular dichroism spectra of the species and the theoretical spectra generated by considering the simultaneous weighted contributions of the concomitant monomers and dimers. |
| Databáze: | OpenAIRE |
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