Hostname: page-component-586b7cd67f-t7fkt Total loading time: 0 Render date: 2024-11-24T10:43:01.443Z Has data issue: false hasContentIssue false
  • English
  • Français

Adsorption and Spectroscopic Studies on the Interactions of Cobalt(III) Chelates with Clays

Published online by Cambridge University Press:  28 February 2024

Masami Kaneyoshi ,
Akihiko Yamagishi ,
Masahiro Tanaguchi  and
Akiko Aramata
Masami Kaneyoshi*
Affiliation:
Department of Chemistry, College of Arts and Sciences, The University of Tokyo Komaba, Meguro-ku, Tokyo 153, Japan
Akihiko Yamagishi
Affiliation:
Department of Polymer Sciences, Faculty of Sciences, Hokkaido University, Sapporo 060, Japan
Masahiro Tanaguchi
Affiliation:
Department of Polymer Sciences, Faculty of Sciences, Hokkaido University, Sapporo 060, Japan
Akiko Aramata
Affiliation:
Catalysis Research Center, Hokkaido University, Sapporo 060, Japan
*
4Present address: Laboratory of Magnetic Materials, Shin-Etsu Co. Ltd., Takefu 915, Japan.
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The interactions of the following three kinds of racemic and enantiomeric cobalt(III) chelates with montmorillonite and saponite are studied: [Co(en)3]3+ (en = ethylenediamine), [Co(diNOsar)]3+ (diNOsar = (1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo[6,6,6]-eicosane)cobalt(III))and [Co(diAMsar)]3+ (diAMsar = (1,8-diamino-3,6,10,13,16,19-hexaazabicyclo-[6,6,6]eicosane)-cobalt(III)). At neutral pH, these complexes are adsorbed as a trivalent cation up to 90%–100% of the cation exchange capacity of a clay. No difference is observed in the maximum adsorption amount between the racemic and enantiomeric isomers. The basal spacings of the clay-chelate adducts are determined by the X-ray diffraction measurements of non-oriented powder samples: 14.3 Å for [Co(en)3]3+ montmorillonite, 16.5 Å for [Co(diNOsar)]3+ montmorillonite, and 16.9 Å for [Co(diAMsar)]3+ montmorillonite. The results imply that the chelates form a monolayer in the interlayer space. From the one-dimensional Fourier analyses of the diffraction pattern of [Co(diNOsar)]3+ montmorillonite, the chelate is concluded to be adsorbed with its three-fold symmetry axis in parallel with the layer surface. This is in contrast with the previous results of [Ru(phen)3]2+ and [Ru(bpy)3]2+, which are adsorbed with their three-fold symmetry axes perpendicular to the surface. The conclusion is consistent with the angular dependence of the infrared absorption spectrum of the film of the adduct.

Keywords

Clay-metal chelate interactions
Type
Research Article
Information
Clays and Clay Minerals , Volume 41 , Issue 1 , February 1993 , pp. 1 - 6
Copyright
Copyright © 1993, The Clay Minerals Society

References

Bailey, S. W., Brindley, G. W. and Brown, G., 1984 Structure of layer silicates Crystal Structure of Clay Minerals and Their X-ray Identification London Mineralogical Society.Google Scholar
Fripiat, J. J., 1986 Internal surface of clays and constrained chemical reactions Clays & Clay Minerals 34 501 – 506 10.1346/CCMN.1986.0340501.CrossRefGoogle Scholar
Geue, R. J., Hambley, T. W., Harrowfield, J. M., Sargeson, A. M. and Snow, M. R., 1984 Metal ion encapsulation: Cobalt cages derived from polyamines, formaldehyde, and nitrometane J. Amer. Chem. Soc 106 5478 – 5488 10.1021/ja00331a016.CrossRefGoogle Scholar
Nakamura, Y., Yamagishi, A. and Koga, Y., 1988 Adsorption properties of montmorillonite and synthetic saponite as packing materials in liquid column chromatography Clays & Clay Minerals 36 530 – 536 10.1346/CCMN.1988.0360606.CrossRefGoogle Scholar
Silverstein, R. M., Bassler, G. C. and Morrill, T. C., 1974 Spectrometric Identification of Organic Compounds New York John Wiley & Sons Inc..Google Scholar
Sutubican, V. and Roy, R., 1961 Isomorphous substitution and infrared spectra of the layer-lattice silicates Amer. Mineral 46 32 – 51.Google Scholar
Thomas, J. K., 1988 Photophysical and photochemical processes on clay surfaces Acc. Chem. Res 21 275 – 280 10.1021/ar00151a004.CrossRefGoogle Scholar
Villemure, G., 1991 X-ray diifraction patterns of montmorillonite oriented films exchanged with enantiomeric and racemic tris(2,2′-bipyridyl)ruthenium(II) Clays & Clay Minerals 39 580 – 585 10.1346/CCMN.1991.0390603.CrossRefGoogle Scholar
Villemure, G. and Bard, A. J., 1990 Clay modified electrode: Pt. 10. Studies of clay-adsorbed Ru(bpy)2+ enanti-omers by UV-visible spectroscopy and cyclic voltammetry J. Electroanal. Chem 283 403 – 420 10.1016/0022-0728(90)87404-8.CrossRefGoogle Scholar
Yamagishi, A., 1987 Optical resolution and asymmetric syntheses by use of adsorption on clay minerals J. Coord. Chem 16 131 – 211 10.1080/00958978708081202.CrossRefGoogle Scholar