Complexes of the H5O2+ and H3O+ cations with polyethers in water saturated dichloroethane solutions. A combined IR spectroscopic and quantum mechanics study

A. Varnek; G. Wipff; A. Famulari; M. Raimondi; T. Vorob'eva; E. Stoyanov

doi:10.1039/B201034H

Complexes of the H₅O₂⁺ and H₃O⁺cations with polyethers in water saturated dichloroethane solutions. A combined IR spectroscopic and quantum mechanics study†

A. Varnek,^a G. Wipff,*^a A. Famulari,^b M. Raimondi,^b T. Vorob'eva^c and E. Stoyanov^c

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* Corresponding authors

^a Laboratoire MSM, UMR 7551 CNRS, 4, rue Strasbourg, France

^b Department of Physical Chemistry and Electrochemistry, University of Milan, via Goldi 19, Milan, Italy

^c Institute of Catalysis, Russian Academy of Sciences, av. Lavrentiev, 5, Novosibirsk, Russia

Abstract

We report combined IR spectroscopic and quantum mechanical studies on the interactions between hydrated proton (H₃O⁺ and H₅O₂⁺) and polyethers (L = 15-crown-5, 18-crown-6, benzo-18-crown-6 and polyethylene glycols PEG-400 and PEG-600) in 1,2-dichloroethane (DCE) solution saturated with water, in the presence of non-coordinating chlorinated cobalt dicarbollide anions. The state of the hydrated proton and composition of the complexes are shown to depend on the nature and concentration of the ligand. Thus, 15-crown-5 forms [H₃O⁺·L] and [H₅O₂⁺·2L] complexes at small and high concentrations of L, respectively. At all studied concentrations, 18-crown-6 and benzo-18-crown-6 form only [H₃O⁺·L] type complexes, whereas PEGs form 1 ∶ 1 complexes with H₅O₂⁺. The coordination patterns of the hydrated proton depend on the topology, flexibility/rigidity and the number of donor centres of L. In the [H₃O⁺·(18c6)], [H₃O⁺·(B18c6)] and [H₅O₂⁺·2(15c5)] complexes, the hydrated proton forms preferentially O–H⋯O_L linear hydrogen bonds. In [H₃O⁺·15c5], H₃O⁺ interacts with all 5 O-atoms of 15c5 via one linear and two asymmetric bifurcated H-bonds. We also report the first IR characterization of the [H₅O₂⁺·4H₂O] cation complex in an organic solution.

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Article information

DOI: https://doi.org/10.1039/B201034H
Article type: Paper
Submitted: 28 Jan 2002
Accepted: 08 Mar 2002
First published: 02 Apr 2002

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J. Chem. Soc., Perkin Trans. 2, 2002, 887-893

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Complexes of the H₅O₂⁺ and H₃O⁺ cations with polyethers in water saturated dichloroethane solutions. A combined IR spectroscopic and quantum mechanics study

A. Varnek, G. Wipff, A. Famulari, M. Raimondi, T. Vorob'eva and E. Stoyanov, J. Chem. Soc., Perkin Trans. 2, 2002, 887 DOI: 10.1039/B201034H

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Journal of the Chemical Society, Perkin Transactions 2