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

Lade...
Vorschaubild
Dateien
Zu diesem Dokument gibt es keine Dateien.
Datum
2005
Autor:innen
Drexler, Matthias
Yu, Sze-Man
Beckmann, Henning
Herausgeber:innen
Kontakt
ISSN der Zeitschrift
Electronic ISSN
ISBN
Bibliografische Daten
Verlag
Schriftenreihe
Auflagebezeichnung
ArXiv-ID
Internationale Patentnummer
Angaben zur Forschungsförderung
Projekt
Open Access-Veröffentlichung
Sammlungen
Core Facility der Universität Konstanz
Gesperrt bis
Titel in einer weiteren Sprache
Forschungsvorhaben
Organisationseinheiten
Zeitschriftenheft
Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published
Erschienen in
Journal of Organometallic Chemistry. 2005, 690(16), pp. 3700-3713. ISSN 0022-328X. Available under: doi: 10.1016/j.jorganchem.2005.03.070
Zusammenfassung

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.

Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
540 Chemie
Schlagwörter
Allenylidene complexes, Chromium, Tungsten, Substitution, Propadienylidene complexes
Konferenz
Rezension
undefined / . - undefined, undefined
Zitieren
ISO 690DREXLER, 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. 2005, 690(16), pp. 3700-3713. ISSN 0022-328X. Available under: doi: 10.1016/j.jorganchem.2005.03.070
BibTex
@article{Drexler2005Bisam-22837,
  year={2005},
  doi={10.1016/j.jorganchem.2005.03.070},
  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},
  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: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/server/rdf/resource/123456789/22837">
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-31T16:30:03Z</dc:date>
    <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>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/22837"/>
    <dc:contributor>Fischer, Helmut</dc:contributor>
    <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>
    <dcterms:issued>2005</dcterms:issued>
    <dc:creator>Beckmann, Henning</dc:creator>
    <dc:contributor>Yu, Sze-Man</dc:contributor>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:language>eng</dc:language>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dc:creator>Yu, Sze-Man</dc:creator>
    <dc:contributor>Weibert, Bernhard</dc:contributor>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-31T16:30:03Z</dcterms:available>
    <dc:contributor>Beckmann, Henning</dc:contributor>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:contributor>Haas, Thomas</dc:contributor>
    <dc:rights>terms-of-use</dc:rights>
    <dc:creator>Weibert, Bernhard</dc:creator>
    <dc:creator>Haas, Thomas</dc:creator>
    <dc:creator>Fischer, Helmut</dc:creator>
    <dcterms:bibliographicCitation>Journal of Organometallic Chemistry ; 690 (2005), 16. - S. 3700-3713</dcterms:bibliographicCitation>
    <dc:creator>Drexler, Matthias</dc:creator>
    <dc:contributor>Drexler, Matthias</dc:contributor>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
  </rdf:Description>
</rdf:RDF>
Interner Vermerk
xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter
Kontakt
URL der Originalveröffentl.
Prüfdatum der URL
Prüfungsdatum der Dissertation
Finanzierungsart
Kommentar zur Publikation
Allianzlizenz
Corresponding Authors der Uni Konstanz vorhanden
Internationale Co-Autor:innen
Universitätsbibliographie
Ja
Begutachtet
Diese Publikation teilen