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Springer (part of Springer Nature), Journal of Molecular Modeling, 10(19), p. 4139-4145

DOI: 10.1007/s00894-012-1682-y

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Enhancing and modulating the intrinsic acidity of imidazole and pyrazole through beryllium bonds

Journal article published in 2013 by Otilia Mó ORCID, Manuel Yáñez ORCID, Ibon Alkorta ORCID, José Elguero
This paper is available in a repository.
This paper is available in a repository.

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Abstract

The structure and electronic properties of the complexes formed by the interaction of imidazole and pyrazole with different BeXH(BeX(2)) (X = H, Me, F, Cl) derivatives have been investigated via B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) calculations. The formation of these azole:BeXH(BeX(2)) complexes is accompanied by a dramatic enhancement of the intrinsic acidity of the azole, as the deprotonated azole is much more stable after the aforementioned interaction. Most importantly, the increase in acidity is so large that the azole:BeXH or azole:BeX(2) complexes behave as NH acids, which are stronger than typical oxyacids such as phosphoric acid and oxalic acid. Interestingly, the increase in acidity can be tuned through appropriate selection of the substituents attached to the Be atom, permitting us to modulate the electron-accepting ability of the BeXH or BeX(2) molecule.