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Bis(amino)allenylidene complexes by displacement of the MeO group in methoxy allenylidene complexes of chromium and tungsten : Synthesis, DFT calculations and solid-state structures of new bis(amino)allenylidene complexes

Bis(amino)allenylidene complexes by displacement of the MeO group in methoxy allenylidene complexes of chromium and tungsten : Synthesis, DFT calculations and solid-state structures of new bis(amino)allenylidene complexes

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DREXLER, Matthias, Thomas HAAS, Sze-Man YU, Henning BECKMANN, Bernhard WEIBERT, Helmut FISCHER, 2005. Bis(amino)allenylidene complexes by displacement of the MeO group in methoxy allenylidene complexes of chromium and tungsten : Synthesis, DFT calculations and solid-state structures of new bis(amino)allenylidene complexes. In: Journal of Organometallic Chemistry. 690(16), pp. 3700-3713. ISSN 0022-328X. Available under: doi: 10.1016/j.jorganchem.2005.03.070

@article{Drexler2005Bisam-22837, title={Bis(amino)allenylidene complexes by displacement of the MeO group in methoxy allenylidene complexes of chromium and tungsten : Synthesis, DFT calculations and solid-state structures of new bis(amino)allenylidene complexes}, year={2005}, doi={10.1016/j.jorganchem.2005.03.070}, number={16}, volume={690}, issn={0022-328X}, journal={Journal of Organometallic Chemistry}, pages={3700--3713}, author={Drexler, Matthias and Haas, Thomas and Yu, Sze-Man and Beckmann, Henning and Weibert, Bernhard and Fischer, Helmut} }

<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/123456789/22837"> <dc:contributor>Drexler, Matthias</dc:contributor> <dcterms:issued>2005</dcterms:issued> <dcterms:bibliographicCitation>Journal of Organometallic Chemistry ; 690 (2005), 16. - S. 3700-3713</dcterms:bibliographicCitation> <dc:contributor>Yu, Sze-Man</dc:contributor> <dc:contributor>Beckmann, Henning</dc:contributor> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dc:creator>Yu, Sze-Man</dc:creator> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dcterms:title>Bis(amino)allenylidene complexes by displacement of the MeO group in methoxy allenylidene complexes of chromium and tungsten : Synthesis, DFT calculations and solid-state structures of new bis(amino)allenylidene complexes</dcterms:title> <dc:creator>Drexler, Matthias</dc:creator> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-31T16:30:03Z</dcterms:available> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <dc:contributor>Fischer, Helmut</dc:contributor> <dc:language>eng</dc:language> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dc:contributor>Haas, Thomas</dc:contributor> <dc:contributor>Weibert, Bernhard</dc:contributor> <dc:creator>Weibert, Bernhard</dc:creator> <dc:creator>Fischer, Helmut</dc:creator> <dc:creator>Haas, Thomas</dc:creator> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-31T16:30:03Z</dc:date> <dc:rights>deposit-license</dc:rights> <dc:creator>Beckmann, Henning</dc:creator> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/22837"/> <dcterms:abstract xml:lang="eng">Pentacarbonyl dimethylamino(methoxy)allenylidene tungsten, [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OMe)NMe2] (1b), reacts with one equivalent of primary amines, H2NR, by selectively replacing the methoxy group to give dimethylamino(amino)allenylidene complexes, [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(NHR)NMe2]. When the amine is used in excess both terminal groups, OMe as well as NMe2, are replaced by the primary amino group giving [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(NHR)2 ]. The NHR substituent in these complexes may be modified by deprotonation with LDA followed by alkylation. The replacement of the methoxy group in 1b by a secondary amino group, NR2, can be achieved by a stepwise process. Addition of Li[NR2] to the Cγ atom of 1b affords an alkynyl tungstate. Subsequent OMe− elimination induced by TMS-Cl/SiO2 yields the allenylidene complexes [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(NR2)NMe2]. When bidentate diamines are used instead of monoamines both substituents, OMe and NMe2, are replaced and allenylidene complexes are formed in which Cγ constitutes part of a 5-, 6-, or 7-membered heterocycle. The reaction of [(CO)5Crdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OMe)NMe2] (1a) with diethylene triamine affords an allenylidene complex with a heterocyclic endgroup carrying a dangling CH2CH2NH2 substituent. All reactions follow a strict regioselective attack of the nucleophile at Cγ and proceed with good to excellent yields. The addition of N–H to the Cαdouble bond; length as m-dashCβ bond is not observed. By applying either one of these routes nearly any substitution pattern in bis(amino)allenylidene complex can be realized.</dcterms:abstract> </rdf:Description> </rdf:RDF>

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