Complexes of the H(5)O(2)(+) and H(3)O(+) Cations with Polyethers in Water Saturated Dichloroethane Solutions. A Combined IR Spectroscopic and Quantum Mechanics Study
Full article
| Common |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Journal of the Chemical Society. Perkin Transactions 2 (up to 2002)
ISSN: 0300-9580
|
| Output data |
Year: 2002,
Number: 5,
Pages: 887-893
Pages count
: 7
DOI:
10.1039/b201034h
|
| Tags |
Complexation; Composition; Ethane; Hydration; Hydrogen bonds; Infrared spectroscopy; Negative ions; Protons; Quantum theory; Solutions |
| Authors |
Varnek A.
1
,
Wipff G.
1
,
Famulari A.
2
,
Raimondi M.
2
,
Vorob'eva T.
3
,
Stoyanov E.
3
|
| Affiliations |
| 1 |
Laboratoire MSM, UMR 7551 CNRS, 4, rue Strasbourg, 67000, France
|
| 2 |
Department of Physical Chemistry and Electrochemistry, University of Milan, via Goldi 19, Milan, Italy
|
| 3 |
Institute of Catalysis, Russian Academy of Sciences, av. Lavrentiev, 5, Novosibirsk, Russia
|
|
Funding (1)
|
1
|
European Commission
|
INCO-COPERNICUS ERB IC15-CT98-0208
|
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⋯OL 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.