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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.
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Abstract

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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

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