Theoretical study of the first step of SPLET mechanism: O–H bond cleavage in the mono-substituted benzoic acids
Department of Chemical Physics, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovakia
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Abstract: The first step of SPLET mechanism in solution phase for 15 benzoic acid derivatives was studied from the thermodynamic point of view. For this purpose, proton affinities (PAs) of corresponding carboxylate or phenoxide anions were computed by means of DFT method employing B3LYP and M062X functionals with 6-311++G** basis set and SMD or IEF-PCM solvent model. The substituent effect on PAs was analyzed in terms of Hammett constants, σp. Found dependences exhibit satisfactory linearity and enable quick estimation of solution phase PAs from the Hammett constants.
Keywords: Proton affinity, B3LYP, M062X, IEF-PCM, SMD, benzoic acid derivatives
Full paper in Portable Document Format: acs_0219.pdf
Acta Chimica Slovaca, Vol. 8, No. 2, 2015, pp. 120—125, DOI: DOI: 10.1515/acs-2015-0021