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Selenobenzaldehyd-Komplexe von Chrom und Wolfram : Synthese, Struktur und η1/η2-Isomerie

Selenobenzaldehyd-Komplexe von Chrom und Wolfram : Synthese, Struktur und η1/η2-Isomerie

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FISCHER, Helmut, Siegfried ZEUNER, Ulrike GERBING, Jürgen RIEDE, Cornelius G. KREITER, 1989. Selenobenzaldehyd-Komplexe von Chrom und Wolfram : Synthese, Struktur und η1/η2-Isomerie. In: Journal of Organometallic Chemistry. 377(1), pp. 105-122. ISSN 0022-328X. eISSN 1872-8561. Available under: doi: 10.1016/0022-328X(89)80056-7

@article{Fischer1989Selen-23500, title={Selenobenzaldehyd-Komplexe von Chrom und Wolfram : Synthese, Struktur und η1/η2-Isomerie}, year={1989}, doi={10.1016/0022-328X(89)80056-7}, number={1}, volume={377}, issn={0022-328X}, journal={Journal of Organometallic Chemistry}, pages={105--122}, author={Fischer, Helmut and Zeuner, Siegfried and Gerbing, Ulrike and Riede, Jürgen and Kreiter, Cornelius G.} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/23500"> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dc:contributor>Zeuner, Siegfried</dc:contributor> <dc:language>eng</dc:language> <dcterms:title>Selenobenzaldehyd-Komplexe von Chrom und Wolfram : Synthese, Struktur und η1/η2-Isomerie</dcterms:title> <dcterms:issued>1989</dcterms:issued> <dc:rights>terms-of-use</dc:rights> <dcterms:rights rdf:resource="https://kops.uni-konstanz.de/page/termsofuse"/> <dcterms:bibliographicCitation>Journal of Organometallic Chemistry ; 377 (1989), 1. - S. 105-122</dcterms:bibliographicCitation> <dc:creator>Zeuner, Siegfried</dc:creator> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-06-28T14:11:32Z</dc:date> <dc:creator>Riede, Jürgen</dc:creator> <dc:contributor>Riede, Jürgen</dc:contributor> <dc:contributor>Fischer, Helmut</dc:contributor> <dc:contributor>Gerbing, Ulrike</dc:contributor> <dc:contributor>Kreiter, Cornelius G.</dc:contributor> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/23500"/> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:creator>Kreiter, Cornelius G.</dc:creator> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-06-28T14:11:32Z</dcterms:available> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dc:creator>Gerbing, Ulrike</dc:creator> <dcterms:abstract xml:lang="eng">The benzylidene(pentacarbonyl)chromium and -tungsten complexes (CO)5M-[C(C6H4R-p)H] (II) (M = Cr: R = H (a), OMe (b); M = W: R = CF3 (c), H (d), Me (e), OMe (f), OEt (g)) react with [NEt4]SeCN by insertion of the selenium atom into the metal-benzylidene carbon bond to give pentacarbonyl(selenobenzaldehyde) complexes, (CO)5M[Se=C(C6H4R-p)H] (IIIa-g). The IR spectra of η1-III and η2-III differ significantly. In solution the compounds are present in the form of a dynamic equilibrium between the η2- and the η1-isomers. At room temperature the interconversion of the isomers is rapid on the 1H NMR time scale. Two isomers for IIIe can be detected below - 113°C. The η1/η2-isomeric equilibrium shifts toward the η2-isomer (a) with decreasing electron-donating ability of the para-substituent R, (b) with decreasing temperature, (c) with decreasing polarity of the solvent and, (d) by replacement of chromium with tungsten in analogous complexes. The structure of η2-IIId was established by X-ray crystallography. The difference in enthalpy (ΔH) and entropy (ΔS) between the η1- and the η2-isomers in toluene solution has been determined. ΔS is small and almost independent of the substituents R. ΔH for the rearrangement η2-III → η1-III decreases in the series IIIc, d, e and is negative for IIIf. The equilibrium constants are mainly determined by the donor / acceptor properties of R.</dcterms:abstract> <dc:creator>Fischer, Helmut</dc:creator> </rdf:Description> </rdf:RDF>

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