@article{Reichmann2011Amino-19739,
  year={2011},
  doi={10.1021/om101163j},
  title={Amino-substituted butatrienes : Unusual η<sup>1</sup> ligands formed by an unusual reaction},
  number={5},
  volume={30},
  issn={0276-7333},
  journal={Organometallics},
  pages={1215--1223},
  author={Reichmann, Bernhard and Drexler, Matthias and Weibert, Bernhard and Szesni, Normen and Strittmatter, Tobias 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/server/rdf/resource/123456789/19739">
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dc:creator>Weibert, Bernhard</dc:creator>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2012-07-20T19:17:52Z</dc:date>
    <dc:contributor>Strittmatter, Tobias</dc:contributor>
    <dc:creator>Szesni, Normen</dc:creator>
    <dc:creator>Reichmann, Bernhard</dc:creator>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2012-10-31T23:25:04Z</dcterms:available>
    <dc:contributor>Reichmann, Bernhard</dc:contributor>
    <dc:contributor>Drexler, Matthias</dc:contributor>
    <dcterms:abstract xml:lang="eng">The reaction of the bis(amino)allenylidene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W═C═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;] with diethyldiazomethane yields two products, a cyclic carbene complex (2) by 1,2-addition of Et&lt;sub&gt;2&lt;/sub&gt;C−N&lt;sub&gt;2&lt;/sub&gt; to the C&lt;sub&gt;α&lt;/sub&gt;−C&lt;sub&gt;β&lt;/sub&gt; bond of the allenylidene ligand and the η&lt;sup&gt;1&lt;/sup&gt;-butatriene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W{C[C(NMe&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]═C═CEt&lt;sub&gt;2&lt;/sub&gt;}] (3). Complex 2 slowly eliminates N&lt;sub&gt;2&lt;/sub&gt; and rearranges into 3. In contrast, only η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes, [(CO)&lt;sub&gt;5&lt;/sub&gt;M{C[C(NMe&lt;sub&gt;2&lt;/sub&gt;)XR]═C═C(R′)&lt;sub&gt;2&lt;/sub&gt;}], are isolated from the reaction of diazoalkanes (R′)&lt;sub&gt;2&lt;/sub&gt;C−N&lt;sub&gt;2&lt;/sub&gt; (R′ = Me, Et, &lt;sup&gt;n&lt;/sup&gt;Pr) with alkoxy(amino)allenylidene complexes [(CO)&lt;sub&gt;5&lt;/sub&gt;M═C═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)OR] (M = Cr, W; R = Me, Et, (−)-menthyl) or with the (alkylthio)(amino)allenylidene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W═C═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)S&lt;sup&gt;n&lt;/sup&gt;Pr]. These new η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes are related to C&lt;sub&gt;α&lt;/sub&gt; phosphine adducts of allenylidene complexes such as [(CO)&lt;sub&gt;5&lt;/sub&gt;W{C(PMe&lt;sub&gt;3&lt;/sub&gt;)═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)Ph}] (17) and might be regarded as C&lt;sub&gt;α&lt;/sub&gt; carbene adducts. However, the PMe&lt;sub&gt;3&lt;/sub&gt; substituent in 17 is not replaced when 17 is treated with an N-heterocyclic carbene. Vice versa, the “carbene” substituent “C(NMe&lt;sub&gt;2&lt;/sub&gt;)OEt” in the η&lt;sup&gt;1&lt;/sup&gt;-butatriene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;Cr{C[C(NMe&lt;sub&gt;2&lt;/sub&gt;)OEt]═C═CEt&lt;sub&gt;2&lt;/sub&gt;}] is not replaceable by PMe&lt;sub&gt;3&lt;/sub&gt;. Free N-heterocyclic carbenes do not add to the C&lt;sub&gt;α&lt;/sub&gt; atom of the allenylidene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W═C═C═C(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;NMe&lt;sub&gt;2&lt;/sub&gt;-p)&lt;sub&gt;2&lt;/sub&gt;] but instead to the C&lt;sub&gt;γ&lt;/sub&gt; atom, giving the dipolar neutral alkynyl complexes [(CO)&lt;sub&gt;5&lt;/sub&gt;W−C≡CC(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;NMe&lt;sub&gt;2&lt;/sub&gt;-p)&lt;sub&gt;2&lt;/sub&gt;L] (L = SIMe, SIMes). DFT calculations on the reaction mechanism indicate that a cyclic carbene complex and two isomeric η&lt;sup&gt;2&lt;/sup&gt;-butatriene complexes are intermediates in the reaction pathway to form η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes. The structure of two representative examples of η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes and of one C&lt;sub&gt;γ&lt;/sub&gt; carbene adduct has been established by X-ray structure analyses.</dcterms:abstract>
    <dc:contributor>Szesni, Normen</dc:contributor>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:contributor>Fischer, Helmut</dc:contributor>
    <dcterms:bibliographicCitation>Publ. in: Organometallics ; 30 (2011), 5. - pp. 1215-1223</dcterms:bibliographicCitation>
    <dcterms:title>Amino-substituted butatrienes : Unusual η&lt;sup&gt;1&lt;/sup&gt; ligands formed by an unusual reaction</dcterms:title>
    <dc:creator>Strittmatter, Tobias</dc:creator>
    <dc:creator>Drexler, Matthias</dc:creator>
    <dc:language>eng</dc:language>
    <dc:rights>terms-of-use</dc:rights>
    <dc:contributor>Weibert, Bernhard</dc:contributor>
    <dc:creator>Fischer, Helmut</dc:creator>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/19739"/>
    <dcterms:issued>2011</dcterms:issued>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
  </rdf:Description>
</rdf:RDF>