Unprecedented Allenylidene Transfer from Chromium to Tungsten

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SZESNI, Normen, Matthias DREXLER, Helmut FISCHER, 2006. Unprecedented Allenylidene Transfer from Chromium to Tungsten. In: Organometallics. 25(16), pp. 3989-3995. ISSN 0276-7333. eISSN 1520-6041

@article{Szesni2006Unpre-22891, title={Unprecedented Allenylidene Transfer from Chromium to Tungsten}, year={2006}, doi={10.1021/om0603969}, number={16}, volume={25}, issn={0276-7333}, journal={Organometallics}, pages={3989--3995}, author={Szesni, Normen and Drexler, Matthias and Fischer, Helmut} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/22891"> <dcterms:abstract xml:lang="eng">Pyrimidylallenylidene complexes 1 M = Cr (a), W (b)) were prepared in a one-pot procedure from readily available 2-ethynylpyrimidine, butyllithium, [(CO)5M(THF)], and triethyloxonium tetrafluoroborate. In addition to 1a,b, the homobinuclear allenylidene complexes 2a,b M = Cr, W) were formed. In 2a,b the second (CO)5M moiety is attached to the nonalkylated nitrogen atom of the pyrimidyl ring. Treatment of the chromium complex 1a with an excess of [(CO)5W(THF)] afforded the tungsten allenylidene complex 2b by transmetalation of the allenylidene ligand and addition of (CO)5W. The allenylidene ligands of other chromium allenylidene complexes [(CO)5CrCCC(R1)R2] could likewise be transferred to tungsten. In contrast, the reverse transmetalation from tungsten to chromium could not be achieved. DFT calculations indicate that the reaction proceeds by an associative rather than a dissociative pathway. The initiating reaction step is coordination of a (CO)5W fragment to the Cα−Cβ bond of the allenylidene ligand.</dcterms:abstract> <dc:contributor>Drexler, Matthias</dc:contributor> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/22891"/> <dc:rights>deposit-license</dc:rights> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-27T06:23:37Z</dcterms:available> <dcterms:title>Unprecedented Allenylidene Transfer from Chromium to Tungsten</dcterms:title> <dc:language>eng</dc:language> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-27T06:23:37Z</dc:date> <dc:contributor>Szesni, Normen</dc:contributor> <dc:creator>Fischer, Helmut</dc:creator> <dc:creator>Szesni, Normen</dc:creator> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <dc:contributor>Fischer, Helmut</dc:contributor> <dcterms:issued>2006</dcterms:issued> <dc:creator>Drexler, Matthias</dc:creator> <dcterms:bibliographicCitation>Organometallics ; 25 (2006), 16. - S. 3989-3995</dcterms:bibliographicCitation> </rdf:Description> </rdf:RDF>

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