Hostname: page-component-586b7cd67f-g8jcs Total loading time: 0 Render date: 2024-11-27T12:33:55.606Z Has data issue: false hasContentIssue false

Reactions of smectites with binuclear oxobridged iron complexes of N-alkyl-N,N-bis (2-pyridylmethyl)amines

Published online by Cambridge University Press:  09 July 2018

S. Dick
Affiliation:
Institut für Anorganisehe Chemie der Universität Münehen, Meiserstraβe 1, D-80333 Münehen, Germany
A. Weiss
Affiliation:
Institut für Anorganisehe Chemie der Universität Münehen, Meiserstraβe 1, D-80333 Münehen, Germany

Abstract

Cationic binuclear oxo- and carboxylate bridged Fe(III) complexes of N-alkyl-N,Nbis(2-pyridylmethyl)amines are introduced into the interlayer region of smectites by cation exchange reactions. The reaction can be divided into three steps. After a predominant loading of external surfaces, cation exchange sites at internal surfaces react, accompanied by considerable stmctaral expansion. Both reaction stages belong to the steep section of the exchange isotherms. At a certain loading, which depends on the complex substituents and the layer charge of the smectite, the isotherms become flat. With bulky shaped complex cations and highly charged smectites, exchange is not quantitative; vermiculite-type minerals show a very small complex uptake. For this behaviour, both thermodynamic and kinetic reasons must be considered. From these results the number of cation exchange positions at external surfaces of smectite crystals may be estimated.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1998

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Dick, S. (1996) Investigations on binuclear oxo-bridged iron complexes and their interaction with smectites. PhD thesis, Univ. Munich, Germany.Google Scholar
Dick, S. & Weiss, A. (1997) Mononuclear and bi nuclear oxo-bridged iron(III) complexes of N-alkyl-N,N-bis( 2-pyridylmethyl)amines. Z. Naturforsch. 52b, 372-384.Google Scholar
Feig, A. & Lippard, S. (1994) Reactions of non-heme iron(II) centers with dioxygen in biology and chemistry. Chem. Rev. 94, 759809.CrossRefGoogle Scholar
Kurtz, D. (1990) Oxo- and hydroxo-bridged diiron complexes: a chemical perspective on a biological unit. Chem. Rev. 90, 585606.Google Scholar
Mehra, O.P. & Jackson, M.C. (1960) Iron removal from soils and clays by a dithionite-citrate system buffered with sodium bicarbonate. Clays Clay Miner. 7, 317327.Google Scholar
Meister, A., Takano, N., Chuard, T., Graf, M., Bernauer, K., Stoeckli-Evans, H. & Stiss-Fink, G. (1995) Synthese und Intercalation der planar-quadratischen Komplexe [Cu(bppep)(H2O)](ClO4)2 und [Ni(bppep)(C1)]C1 (bppep = 2,6-bis[1-phenyl-l- (pyridin-2-yl)ethylpyridin) in Hectorit. Z. anorg. allg. Chem. 621, 117121.CrossRefGoogle Scholar
Que, L. & True, A. (1990) Dinuelear iron- and manganese-oxo sites in biology. Prog. Inorg. Chem.: Bioinorg. Chem. 38, 97200.Google Scholar
Vincent, I., Olivier-Lilley, G. & Averill, B. (1990) Proteins containing oxo-bridged dinuclear iron centers: a bioinorganic perspective. Chem. Rev. 90, 14471467.Google Scholar
Weiss, A. & Hofmann, U. (1951) Batavit. Z. Naturforsch. 6b, 405-409.Google Scholar
Weiss, A. & Sextl, E. (1991) Clay minerals as ion exchangers. Pp. 439–517 in: lon Exchangers. de Gruyter, New York.Google Scholar
Weiss, A. & Dick, S. (1993) Interaction of montmorillonite and beidellite with binuclear iron complexes. Proc. 10th Int. Clay Conf., Adelaide, 161-165.Google Scholar
Weiss, A. & Dick, S. (1994) The binudear Fe(III) complex of N,N,N',N'-tetrakis(2-pyridylmethyl)-2- hydroxy-1,3-diaminopropane – molecular and crystal structure and its interaction with montmorillonite. Z. Naturforsch. 49B, 1051-1058.Google Scholar
Weiss, A. & Dick, S. (1997) Interaction of montmorillonite with hydroxo-bridged binuclear iron complexes and their peroxo adducts. Clay Miner. 32, 135141.Google Scholar