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Exchange and Spectroscopy of Cationic Rhodium Complexes on Hectorite

  • Published:
Clays and Clay Minerals

Abstract

The exchange of Rh(NBD)(Pϕ3)2+, Rh(NBD)(PMe2ϕ)3+, Rh(COD)(Pϕ3)2+, and Rh(PMe2ϕ)4+ on hectorite was studied in methanol/dichloromethane, acetone, dimethylformamide, and acetonitrile. At low initial Rh+ concentration and short contact times, ion exchange was the predominant process, and its selectivity and maximum capacity were solvent-dependent. High initial Rh+ concentrations, long contact times, and the most polar solvents favored intersalation and salt precipitation. In all experiments monolayers of complex formed in the interlamellar space and were very tightly held. The complexes retained their integrity on the surface even after removal of all solvent molecules.

Резюме

Исследовался обмен Rh(NBD)(Pϕ3)2+, Rh(NBD)(PMe2ϕ)3+, Rh(COD)(Pϕ3)2+, и Rh(PMe2ϕ)4+ на гекторите в присутствии метанола/дихлорметана, ацетона, диметилформамида и ацетонитрила. При низких начальных концентрациях Rh+ и небольших временах контакта, ионообмен являлся преобладающим процессом, а его селективность и максимальная способность обмена зависили от типа растворителя. Высокие начальные концентрации Rh+, большие времена контакта и наиболее полярные растворители способствовали пересаливанию и осаждению соли. Во всех экспериментах в межслойной области образовывались монослои комплекса, которые держались очень крепко. Эти комплексы сохраняли свою целостность на поверхности даже после удаления всех молекул растворителя. [E.G.]

Resümee

Der Austausch von Rh(NBD)(Pϕ3)2+, Rh(NBD)(PMe2ϕ)3+, Rh(COD)(Pϕ3)2+, und Rh(PMe2ϕ)4+ an Hektorit wurde in Methanol/Dichloromethan, Aceton, Dimethylformamid, und Acetonitril untersucht. Bei niedriger ursprünglicher Rh+-Konzentration und kurzen Reaktionszeiten fand vor allem Ionenaustausch statt. Die Selektivität und die maximale Kapazität war Lösungsmittelabhängig. Hohe ursprüngliche Rh+-Konzentrationen, lange Reaktionszeiten und die am stärksten polaren Lösungsmittel bewirkten eine überwiegende Versalzung zwischen den Schichten sowie Salzausfällung. In allen Experimenten bildeten sich Einerschichten von Komplexen in den interlamellaren Räumen, die sehr fest gehalten wurden. Die Komplexe blieben auf der Oberfläche unversehrt, selbst dann, wenn alle Lösungsmittelmoleküle entfernt waren. [U.W.]

Résumé

L’échange de [Rh(NBD)(Pϕ3)2]+, [Rh(NBD)(PMe2ϕ)3]+, [Rh(COD)(Pϕ3)2]+ et de [Rh(PMe2ϕ(4]+ sur hectorite a été étudié dans méthanol/dichlorométhane, acétone, diméthylformamide, et acétonitrile. A condition que la concentration initiale de Rh+ est petite et que le temps d’échange et court, l’échange ionique est la réaction majeure. La sélectivité d’échange et la capacité maximale dépendent du solvent. Des grandes concentrations initiales en Rh+, des temps d’échanges longs et les plus polairs solvants favorisent intercalation et précipitation du sel. Dans toutes les expériences une monocouche est formeé dans l’espace interfoliaire. Les complexes retiennent leure identité sur la surface, même après évacuation du solvent.

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  1. Centram voor Oppervlaktescheikunde en Colloïdale Scheikunde, Katholieke Universiteit Leuven, de Croylaan 42, B-3030, Leuven (Heverlee), Belgium

    Robert A. Schoonheydt, Jozefien Pelgrims, Paul Hendrickx & Johan Luts

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  1. Robert A. Schoonheydt
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  2. Jozefien Pelgrims
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  3. Paul Hendrickx
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  4. Johan Luts
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Schoonheydt, R.A., Pelgrims, J., Hendrickx, P. et al. Exchange and Spectroscopy of Cationic Rhodium Complexes on Hectorite. Clays Clay Miner. 32, 185–190 (1984). https://doi.org/10.1346/CCMN.1984.0320305

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  • DOI: https://doi.org/10.1346/CCMN.1984.0320305

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