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Exchange and Spectroscopy of Cationic Rhodium Complexes on Hectorite

Published online by Cambridge University Press:  02 April 2024

Robert A. Schoonheydt ,
Jozefien Pelgrims ,
Paul Hendrickx  and
Johan Luts
Robert A. Schoonheydt
Affiliation:
Centram voor Oppervlaktescheikunde en Colloïdale Scheikunde, Katholieke Universiteit Leuven, de Croylaan 42, B-3030 Leuven (Heverlee), Belgium
Jozefien Pelgrims
Affiliation:
Centram voor Oppervlaktescheikunde en Colloïdale Scheikunde, Katholieke Universiteit Leuven, de Croylaan 42, B-3030 Leuven (Heverlee), Belgium
Paul Hendrickx
Affiliation:
Centram voor Oppervlaktescheikunde en Colloïdale Scheikunde, Katholieke Universiteit Leuven, de Croylaan 42, B-3030 Leuven (Heverlee), Belgium
Johan Luts
Affiliation:
Centram voor Oppervlaktescheikunde en Colloïdale Scheikunde, Katholieke Universiteit Leuven, de Croylaan 42, B-3030 Leuven (Heverlee), Belgium
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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

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

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

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.

Keywords

CatalysisCation exchangeHectoritePhosphineRhodium
Type
Research Article
Information
Clays and Clay Minerals , Volume 32 , Issue 3 , June 1984 , pp. 185 - 190
Copyright
Copyright © 1984, The Clay Minerals Society

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