Donor-substituted allenylidene(carbonyl)(XR 3)chromium complexes (X=P, As, Sb) – synthesis and properties

Kurzanzeige
dc.contributor.authorSzesni, Normendeu
dc.contributor.authorWeibert, Bernhard
dc.contributor.authorFischer, Helmut
dc.date.accessioned2013-05-29T18:09:06Zdeu
dc.date.available2013-05-29T18:09:06Zdeu
dc.date.issued2004
dc.description.abstractPhotolysis of the allenylidene pentacarbonyl chromium complexes [(CO)5Cr=C=C=C(R1)R2] (R1 = NMe2, NPh2; R2 = NMe2, OMe, Ph) in THF in the presence of equimolar amounts of XR3(XR3 = various phosphanes, P(OMe)3, AsPh3, SbPh3) affords cis-allenylidene tetracarbonyl XR3 complexes, cis-[(CO)4(XR3)Cr=C=C=C(R1)R2]. When in the photolysis of [(CO)5Cr=C=C=C(NMe2)Ph], the phosphanes PR3 (R=C6H4F-p, C6H4Cl-p, OMe) are used in excess (three equivalents) two carbonyl ligands are displaced and the mer-tricarbonyl complexes mer-[(CO)3(PR3)2Cr=C=C=C(NMe2)Ph] are formed both PR3 ligands being mutually trans. The structure of the new complexes is established by IR, NMR, and UV–Vis spectroscopy, that of cis-[(CO)4(PPh3)Cr=C=C=C(NMe2)Ph] additionally by an X-ray structural analysis. As indicated by the spectroscopic data of the compounds, these complexes are best described as hybrids of allenylidene and zwitterionic alkynyl complexes with delocalization of the electron pair at nitrogen bonded to the Cγ atom of the allenylidene ligand towards the metal center. The relative contribution of the allenylidene and zwitterionic alkynyl resonance forms is influenced by XR3. Increasing the donor properties of XR3 favors the allenylidene resonance form.eng
dc.description.versionpublished
dc.identifier.citationInorganica Chimica Acta ; 357 (2004), 6. - S. 1789-1798deu
dc.identifier.doi10.1016/j.ica.2003.12.013deu
dc.identifier.urihttp://kops.uni-konstanz.de/handle/123456789/22920
dc.language.isoengdeu
dc.legacy.dateIssued2013-05-29deu
dc.rightsterms-of-usedeu
dc.rights.urihttps://rightsstatements.org/page/InC/1.0/deu
dc.subjectAllenylidene complexesdeu
dc.subjectChromiumdeu
dc.subjectPhosphane complexesdeu
dc.subjectPhotolysisdeu
dc.subjectSubstitutiondeu
dc.subject.ddc540deu
dc.titleDonor-substituted allenylidene(carbonyl)(XR 3)chromium complexes (X=P, As, Sb) – synthesis and propertieseng
dc.typeJOURNAL_ARTICLEdeu
dspace.entity.typePublication
kops.citation.bibtex
@article{Szesni2004Donor-22920,
  year={2004},
  doi={10.1016/j.ica.2003.12.013},
  title={Donor-substituted allenylidene(carbonyl)(XR 3)chromium complexes (X=P, As, Sb) – synthesis and properties},
  number={6},
  volume={357},
  issn={0020-1693},
  journal={Inorganica Chimica Acta},
  pages={1789--1798},
  author={Szesni, Normen and Weibert, Bernhard and Fischer, Helmut}
}
kops.citation.iso690SZESNI, Normen, Bernhard WEIBERT, Helmut FISCHER, 2004. Donor-substituted allenylidene(carbonyl)(XR 3)chromium complexes (X=P, As, Sb) – synthesis and properties. In: Inorganica Chimica Acta. 2004, 357(6), pp. 1789-1798. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2003.12.013deu
kops.citation.iso690SZESNI, Normen, Bernhard WEIBERT, Helmut FISCHER, 2004. Donor-substituted allenylidene(carbonyl)(XR 3)chromium complexes (X=P, As, Sb) – synthesis and properties. In: Inorganica Chimica Acta. 2004, 357(6), pp. 1789-1798. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2003.12.013eng
kops.citation.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/123456789/22920">
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-29T18:09:06Z</dcterms:available>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:contributor>Szesni, Normen</dc:contributor>
    <dc:rights>terms-of-use</dc:rights>
    <dc:language>eng</dc:language>
    <dc:creator>Fischer, Helmut</dc:creator>
    <dc:creator>Szesni, Normen</dc:creator>
    <dcterms:issued>2004</dcterms:issued>
    <dc:contributor>Weibert, Bernhard</dc:contributor>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/22920"/>
    <dc:contributor>Fischer, Helmut</dc:contributor>
    <dc:creator>Weibert, Bernhard</dc:creator>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dcterms:abstract xml:lang="eng">Photolysis of the allenylidene pentacarbonyl chromium complexes [(CO)&lt;sub&gt;5&lt;/sub&gt;Cr=C=C=C(R&lt;sup&gt;1&lt;/sup&gt;)R&lt;sup&gt;2&lt;/sup&gt;] (R&lt;sup&gt;1&lt;/sup&gt; = NMe&lt;sub&gt;2&lt;/sub&gt;, NPh&lt;sub&gt;2&lt;/sub&gt;; R&lt;sup&gt;2&lt;/sup&gt; = NMe&lt;sub&gt;2&lt;/sub&gt;, OMe, Ph) in THF in the presence of equimolar amounts of XR&lt;sub&gt;3&lt;/sub&gt;(XR&lt;sub&gt;3&lt;/sub&gt; = various phosphanes, P(OMe)&lt;sub&gt;3&lt;/sub&gt;, AsPh&lt;sub&gt;3&lt;/sub&gt;, SbPh&lt;sub&gt;3&lt;/sub&gt;) affords cis-allenylidene tetracarbonyl XR&lt;sub&gt;3&lt;/sub&gt; complexes, cis-[(CO)&lt;sub&gt;4&lt;/sub&gt;(XR&lt;sub&gt;3&lt;/sub&gt;)Cr=C=C=C(R&lt;sup&gt;1&lt;/sup&gt;)R&lt;sup&gt;2&lt;/sup&gt;]. When in the photolysis of [(CO)&lt;sub&gt;5&lt;/sub&gt;Cr=C=C=C(NMe&lt;sub&gt;2&lt;/sub&gt;)Ph], the phosphanes PR&lt;sub&gt;3&lt;/sub&gt; (R=C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;F-p, C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;Cl-p, OMe) are used in excess (three equivalents) two carbonyl ligands are displaced and the mer-tricarbonyl complexes mer-[(CO)&lt;sub&gt;3&lt;/sub&gt;(PR&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Cr=C=C=C(NMe&lt;sub&gt;2&lt;/sub&gt;)Ph] are formed both PR3 ligands being mutually trans. The structure of the new complexes is established by IR, NMR, and UV–Vis spectroscopy, that of cis-[(CO)4(PPh3)Cr=C=C=C(NMe2)Ph] additionally by an X-ray structural analysis. As indicated by the spectroscopic data of the compounds, these complexes are best described as hybrids of allenylidene and zwitterionic alkynyl complexes with delocalization of the electron pair at nitrogen bonded to the C&lt;sub&gt;γ&lt;/sub&gt; atom of the allenylidene ligand towards the metal center. The relative contribution of the allenylidene and zwitterionic alkynyl resonance forms is influenced by XR&lt;sub&gt;3&lt;/sub&gt;. Increasing the donor properties of XR&lt;sub&gt;3&lt;/sub&gt; favors the allenylidene resonance form.</dcterms:abstract>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-29T18:09:06Z</dc:date>
    <dcterms:bibliographicCitation>Inorganica Chimica Acta ; 357 (2004), 6. - S. 1789-1798</dcterms:bibliographicCitation>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dcterms:title>Donor-substituted allenylidene(carbonyl)(XR 3)chromium complexes (X=P, As, Sb) – synthesis and properties</dcterms:title>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
  </rdf:Description>
</rdf:RDF>
kops.flag.knbibliographytrue
kops.identifier.nbnurn:nbn:de:bsz:352-229204deu
kops.sourcefieldInorganica Chimica Acta. 2004, <b>357</b>(6), pp. 1789-1798. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2003.12.013deu
kops.sourcefield.plainInorganica Chimica Acta. 2004, 357(6), pp. 1789-1798. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2003.12.013deu
kops.sourcefield.plainInorganica Chimica Acta. 2004, 357(6), pp. 1789-1798. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2003.12.013eng
kops.submitter.emailkarin.hoch@uni-konstanz.dedeu
relation.isAuthorOfPublicationb63fe83b-d2d6-466a-990d-628735d6d149
relation.isAuthorOfPublication726c19aa-617a-4eb9-9a10-3747eff2ffc8
relation.isAuthorOfPublication.latestForDiscoveryb63fe83b-d2d6-466a-990d-628735d6d149
source.bibliographicInfo.fromPage1789
source.bibliographicInfo.issue6
source.bibliographicInfo.toPage1798
source.bibliographicInfo.volume357
source.identifier.issn0020-1693
source.periodicalTitleInorganica Chimica Acta

Dateien

Lizenzbündel

Gerade angezeigt 1 - 1 von 1
Vorschaubild nicht verfügbar
Name:
license.txt
Größe:
1.92 KB
Format:
Plain Text
Beschreibung:
license.txt
license.txtGröße: 1.92 KBDownloads: 0

Sammlungen

Chemie: Publikationen