Publikation: Donor-substituted allenylidene(carbonyl)(XR 3)chromium complexes (X=P, As, Sb) – synthesis and properties
Dateien
Datum
Autor:innen
Herausgeber:innen
ISSN der Zeitschrift
Electronic ISSN
ISBN
Bibliografische Daten
Verlag
Schriftenreihe
Auflagebezeichnung
URI (zitierfähiger Link)
DOI (zitierfähiger Link)
Internationale Patentnummer
Angaben zur Forschungsförderung
Projekt
Open Access-Veröffentlichung
Sammlungen
Core Facility der Universität Konstanz
Titel in einer weiteren Sprache
Publikationstyp
Publikationsstatus
Erschienen in
Zusammenfassung
Photolysis 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.
Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
Schlagwörter
Konferenz
Rezension
Zitieren
ISO 690
SZESNI, 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.2003.12.013BibTex
@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} }
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)<sub>5</sub>Cr=C=C=C(R<sup>1</sup>)R<sup>2</sup>] (R<sup>1</sup> = NMe<sub>2</sub>, NPh<sub>2</sub>; R<sup>2</sup> = NMe<sub>2</sub>, OMe, Ph) in THF in the presence of equimolar amounts of XR<sub>3</sub>(XR<sub>3</sub> = various phosphanes, P(OMe)<sub>3</sub>, AsPh<sub>3</sub>, SbPh<sub>3</sub>) affords cis-allenylidene tetracarbonyl XR<sub>3</sub> complexes, cis-[(CO)<sub>4</sub>(XR<sub>3</sub>)Cr=C=C=C(R<sup>1</sup>)R<sup>2</sup>]. When in the photolysis of [(CO)<sub>5</sub>Cr=C=C=C(NMe<sub>2</sub>)Ph], the phosphanes PR<sub>3</sub> (R=C<sub>6</sub>H<sub>4</sub>F-p, C<sub>6</sub>H<sub>4</sub>Cl-p, OMe) are used in excess (three equivalents) two carbonyl ligands are displaced and the mer-tricarbonyl complexes mer-[(CO)<sub>3</sub>(PR<sub>3</sub>)<sub>2</sub>Cr=C=C=C(NMe<sub>2</sub>)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<sub>γ</sub> atom of the allenylidene ligand towards the metal center. The relative contribution of the allenylidene and zwitterionic alkynyl resonance forms is influenced by XR<sub>3</sub>. Increasing the donor properties of XR<sub>3</sub> 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>