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Impact of metal cation complexation and protonation on tautomeric and resonance forms of the oxaalkyl Schiff bases derived from 5-substituted salicylaldehyde and 2-hydroxy-1-naphthlaldehyde

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Abstract

Structures of the main resonance and tautomeric forms of three Schiff bases of 2-hydroxy-1-naphthaldehyde (1OXA), 5-bromosalicylaldehyde (2OXA) and 5-nitrosalicylaldehyde (3OXA) with 1,8-diamine-3,6-dioxaoctane, before and after protonation and complexation of monovalent metal cations, have been studied by FTIR, 1H, 13C and 15N NMR methods. The spectroscopic investigations provided clear evidence that the Schiff bases exist in acetonitrile solution as three different tautomers: 1OXA in enamine-oxo, 2OXA in imine-hydroxy and 3OXA in a low-barrier O···H···N imine-oxo forms. It was found on the basis of multinuclear NMR studies, that in solid state, the enamine-oxo and imine-hydroxy tautomers are formed exclusively, but not the untypical imine-oxo tautomer, which requires strong stabilisation by solvent molecules in solution. MOG-PM6 calculations of the different tautomers allowed visualisation of their energetically the most favourable structures. Protonation of 1OXA–3OXA Schiff bases leads to formation of common forms, i.e. protonated imine-hydroxy structure, irrespectively of the structure of tautomer before protonation. In turn, coordination of monovalent metal cations implies common formation of zwitterionic forms within all studied ligands in solution. Application of FT-IR and NMR titrations in combination with ESI MS spectrometry revealed the nature and the structure of OXA complexes, whose formation is impeded by the intra- and intermolecular interactions. MOG-PM6 calculations allowed visualisation of Li+ and Na+ metal coordination sphere geometries within structure of all investigated complexes, stabilised by intermolecular interactions with solvent molecules.

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Acknowledgments

PP, KP and KK wish to thank for the project financial support of the Polish National Science Center (NCN), Grant decision number DEC-2012/05/E/ST5/03792.

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Authors and Affiliations

  1. Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614, Poznan, Poland

    Krystian Pyta, Piotr Przybylski, Katarzyna Klich & Bogumil Brzezinski

  2. Institute of Organic Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224, Warsaw, Poland

    Wojciech Schilf & Bohdan Kamieński

  3. Institute of Physical Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224, Warsaw, Poland

    Bohdan Kamieński

  4. Department of Inorganic and Analytical Chemistry, West Pomeranian University of Technology, al. Piastów 42, 71-065, Szczecin, Poland

    Eugeniusz Grech, Beata Kołodziej & Anna Szady-Chełmieniecka

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  1. Krystian Pyta
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Pyta, K., Przybylski, P., Klich, K. et al. Impact of metal cation complexation and protonation on tautomeric and resonance forms of the oxaalkyl Schiff bases derived from 5-substituted salicylaldehyde and 2-hydroxy-1-naphthlaldehyde. Struct Chem 25, 1733–1746 (2014). https://doi.org/10.1007/s11224-014-0447-x

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