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Publication Type
Journal Article
UWI Author(s)
Author, Analytic
Bakir, Mohammed, A.; Sullivan, B. Patrick; MacKay, S.; Linton, R.; Meyer, T.
Author Affiliation, Ana.
Chemistry; Faculty of Pure and Applied Sciences
Article Title
Coordination chemistry in thin polymeric films poly-[Fe(vbpy)2(CN)2], poly-vbpy: Binding and reduction of [Rh(COD)Cl] and PdCl2
Medium Designator
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Connective Phrase
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Journal Title
Chemistry of Materials
Translated Title
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Reprint Status
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Date of Publication
1996
Volume ID
8
Issue ID
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Page(s)
2461-2467
Language
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Connective Phrase
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Location/URL
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ISSN
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Notes
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Abstract
Thin polymetric films of poly-[Fe(vbpy)2(CN)2], poly-vbpy (vbpy is 4-methyl-4'-vinyl-2,2'-bipyridine) undergo reactions with transition-metal compounds via the cyano groups or the uncoordinated vinyl-1,2'-bipyridine. The reaction between the dicyano/vbpy film and [Rh-(COD)C1]2 led to the incorporation of one or two [Rh(COD)C1] units into the film. Short reaction periods, <0.5 h, led to the incorporation of one [Rh(COD)C1] unit by binding to the uncoordinated vbpy group to give poly-[Fe(vbpy)2(CN)2], poly-[Rh(vbpy)(COD)]C1, a second group is incorporated at >0.5 h by binding one of the cyano groups to give poly-{Fe-(vbpy)2(CN)[CNRh(COD)C1]}, poly-[Rh(vbpy)(COD)C1]C1. Binding sites and composiotions within the films were established by FTIR, UV-visible, and XPS measurements. The dicyano/vbpy films also react with PdC12(PhCN)2 (PhCN = benzonitrile) incorporating two [PdC12] units to give poly-{Fe(vbpy)2(CN)[CNPdC12(NCCH3)]}, poly-Pd(vbpy)C12. PdC12 incorporation is more rapid than [Rh(COD)C1]. Electrochemical reduction of films containing RhI or PdII resulted in the production of Rh0 or Pd0 particles in/on the films. Reduction of a poly-{Fe(vbpy)2(CN)[CNPdC12(NCCH3)}, poly-Pd(vbpy)C12 film with PdC12(PhCN)2 in the external solution led to the of dispersion of Pd0 particles on the film surface as shown by SEM measurements. Films with surface-dispersed palladium or rhodium are active electrocatalysts for the reduction of carbon dioxide....
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Keywords
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