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Redox-Responsive Rhodocenium [O,O], [N,N] and [N,C,N]Metalloligands

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PEVNY, Florian, Rainer WINTER, Daniela EISENSTECKEN, Holger KOPACKA, Barbara ENK, Klaus WURST, Thomas MÜLLER, Benno BILDSTEIN, 2011. Redox-Responsive Rhodocenium [O,O], [N,N] and [N,C,N]Metalloligands. In: European Journal of Inorganic Chemistry. 2011(19), pp. 2958-2966. ISSN 1434-1948. Available under: doi: 10.1002/ejic.201100226

@article{Pevny2011Redox-13940, title={Redox-Responsive Rhodocenium [O,O], [N,N] and [N,C,N]Metalloligands}, year={2011}, doi={10.1002/ejic.201100226}, number={19}, volume={2011}, issn={1434-1948}, journal={European Journal of Inorganic Chemistry}, pages={2958--2966}, author={Pevny, Florian and Winter, Rainer and Eisenstecken, Daniela and Kopacka, Holger and Enk, Barbara and Wurst, Klaus and Müller, Thomas and Bildstein, Benno} }

<rdf:RDF xmlns:dcterms="" xmlns:dc="" xmlns:rdf="" xmlns:bibo="" xmlns:dspace="" xmlns:foaf="" xmlns:void="" xmlns:xsd="" > <rdf:Description rdf:about=""> <dc:contributor>Bildstein, Benno</dc:contributor> <bibo:uri rdf:resource=""/> <dc:creator>Müller, Thomas</dc:creator> <dc:creator>Kopacka, Holger</dc:creator> <dc:creator>Pevny, Florian</dc:creator> <dcterms:isPartOf rdf:resource=""/> <dc:contributor>Enk, Barbara</dc:contributor> <dc:rights>terms-of-use</dc:rights> <dcterms:rights rdf:resource=""/> <dc:creator>Wurst, Klaus</dc:creator> <dcterms:available rdf:datatype="">2011-07-11T09:14:58Z</dcterms:available> <dc:creator>Eisenstecken, Daniela</dc:creator> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:contributor>Wurst, Klaus</dc:contributor> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dc:date rdf:datatype="">2011-07-11T09:14:58Z</dc:date> <dc:language>eng</dc:language> <dc:contributor>Pevny, Florian</dc:contributor> <dcterms:issued>2011</dcterms:issued> <dc:creator>Winter, Rainer</dc:creator> <dc:creator>Bildstein, Benno</dc:creator> <dc:contributor>Müller, Thomas</dc:contributor> <dcterms:title>Redox-Responsive Rhodocenium [O,O], [N,N] and [N,C,N]Metalloligands</dcterms:title> <dc:creator>Enk, Barbara</dc:creator> <dcterms:bibliographicCitation>First publ. in: European Journal of Inorganic Chemistry (2011), 19, pp. 2958–2966</dcterms:bibliographicCitation> <dc:contributor>Winter, Rainer</dc:contributor> <dc:contributor>Eisenstecken, Daniela</dc:contributor> <dc:contributor>Kopacka, Holger</dc:contributor> <dcterms:abstract xml:lang="eng">As we have recently shown, the doubly substituted [1,2-O,O]H, [1,2-O,N]H, [1,2-N,N]H, and [1,3-N,N]H pentafulvenes are convenient N/O-functionalized cyclopentadienide (Cp) precursors. Deprotonation of the pentafulvenes by potassium hydride followed by reaction with [Cp*RhCl2]2 or [Cp*IrCl2]2 gave access to the first functionalized rhodocenium and iridocenium salts that contain two acyl and/or imidoyl substituents. These air-stable compounds represent interesting bis(acyl/imidoyl) or mixed acyl/imidoyl metalloligand systems that combine an axially shielding, electrochemically active metallocene moiety with directly attached, conjugating oxygen and/or nitrogen donor sites. The structural properties of these novel metallocene metalloligands in solution and in the solid state were studied by NMR spectroscopy (1H, 13C, 103Rh) and by single-crystal structure analysis. The electrochemical investigations on complexes 5a, 6b, and 7a showed the effect of the appended functional groups on the potential and on the reversibility of the rhodocenium/rhodocene reduction and provided evidence for the dimerization that followed the reduction. Further redox processes that were due to the heteroatom functions included the stepwise reduction of the 1,2-diketo entity of 5a and the oxidation of the 1,2-diimino moiety of 7a.</dcterms:abstract> <dspace:isPartOfCollection rdf:resource=""/> </rdf:Description> </rdf:RDF>

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