Aminoallenylidene complexes of ruthenium(II) from the regioselective addition of secondary amines to butatrienylidene intermediates: a combined experimental and theoretical study of the hindered rotation around the CN-bond

Lade...
Vorschaubild
Dateien
winter_etal.pdf
winter_etal.pdfGröße: 527.31 KBDownloads: 660
Datum
2003
Autor:innen
Hartmann, Stephan
Zális, Stanislav
Klinkhammer, Karl Wilhelm
Herausgeber:innen
Kontakt
ISSN der Zeitschrift
Electronic ISSN
ISBN
Bibliografische Daten
Verlag
Schriftenreihe
Auflagebezeichnung
DOI (zitierfähiger Link)
ArXiv-ID
Internationale Patentnummer
Angaben zur Forschungsförderung
Projekt
Open Access-Veröffentlichung
Open Access Green
Sammlungen
Core Facility der Universität Konstanz
Gesperrt bis
Titel in einer weiteren Sprache
Forschungsvorhaben
Organisationseinheiten
Zeitschriftenheft
Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published
Erschienen in
Dalton Transactions. 2003(11), pp. 2342-2352. ISSN 1477-9226. Available under: doi: 10.1039/B211774F
Zusammenfassung

Aminoallenylidene complexes trans-[Cl(dppm)2RuC3(NRR )(CH3)] are obtained from the regioselective addition of secondary amines to trans-[Cl(dppm)2Ru C C C CH2] . Unsymmetrically substituted amines give rise to Z/E isomeric mixtures. Dynamic 31P NMR spectroscopy gave an energy barrier of about 85 kJ mol 1 for rotation around the CN-bond pointing to a large contribution of the iminium alkynyl resonance form trans-[Cl(dppm)2Ru–C C– C( NRR )(CH3)] . This is also indicated by the pronounced bond length alternation within the RuC3N-chain as is revealed by X-ray structure analysis of the Z isomer of the (benzylmethyl)methylamine derivative 2d. The issue of NR2 rotation was also addressed by DFT calculations on the trans-[Cl(dhpm)2RuC3{N(CH3)2}(CH3)] model complex (dhpm = H2PCH2PH2). Upon rotation around the iminium type CN bond, the nitrogen lone pair and the π-system of the allenylidene ligand are decoupled, resulting in a significantly longer CN bond and a tetrahedrally coordinated nitrogen atom.

Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
540 Chemie
Schlagwörter
Konferenz
Rezension
undefined / . - undefined, undefined
Zitieren
ISO 690WINTER, Rainer F., Stephan HARTMANN, Stanislav ZÁLIS, Karl Wilhelm KLINKHAMMER, 2003. Aminoallenylidene complexes of ruthenium(II) from the regioselective addition of secondary amines to butatrienylidene intermediates: a combined experimental and theoretical study of the hindered rotation around the CN-bond. In: Dalton Transactions. 2003(11), pp. 2342-2352. ISSN 1477-9226. Available under: doi: 10.1039/B211774F
BibTex
@article{Winter2003Amino-13835,
  year={2003},
  doi={10.1039/B211774F},
  title={Aminoallenylidene complexes of ruthenium(II) from the regioselective addition of secondary amines to butatrienylidene intermediates: a combined experimental and theoretical study of the hindered rotation around the CN-bond},
  number={11},
  issn={1477-9226},
  journal={Dalton Transactions},
  pages={2342--2352},
  author={Winter, Rainer F. and Hartmann, Stephan and Zális, Stanislav and Klinkhammer, Karl Wilhelm},
  note={Supplemental material: http://www.rsc.org/suppdata/dt/b2/b211774f/}
}
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/123456789/13835">
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dcterms:abstract xml:lang="eng">Aminoallenylidene complexes trans-[Cl(dppm)2RuC3(NRR )(CH3)]  are obtained from the regioselective addition of secondary amines to trans-[Cl(dppm)2Ru  C  C  C  CH2] . Unsymmetrically substituted amines give rise to Z/E isomeric mixtures. Dynamic 31P NMR spectroscopy gave an energy barrier of about 85 kJ mol 1 for rotation around the CN-bond pointing to a large contribution of the iminium alkynyl resonance form trans-[Cl(dppm)2Ru–C    C– C(  NRR )(CH3)] . This is also indicated by the pronounced bond length alternation within the RuC3N-chain as is revealed by X-ray structure analysis of the Z isomer of the (benzylmethyl)methylamine derivative 2d. The issue of NR2 rotation was also addressed by DFT calculations on the trans-[Cl(dhpm)2RuC3{N(CH3)2}(CH3)]  model complex (dhpm = H2PCH2PH2). Upon rotation around the iminium type CN bond, the nitrogen lone pair and the π-system of the allenylidene ligand are decoupled, resulting in a significantly longer CN bond and a tetrahedrally coordinated nitrogen atom.</dcterms:abstract>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/13835"/>
    <dc:creator>Klinkhammer, Karl Wilhelm</dc:creator>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-27T12:36:28Z</dc:date>
    <dc:rights>terms-of-use</dc:rights>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/13835/1/winter_etal.pdf"/>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:contributor>Winter, Rainer F.</dc:contributor>
    <dc:creator>Winter, Rainer F.</dc:creator>
    <dc:language>eng</dc:language>
    <dc:creator>Hartmann, Stephan</dc:creator>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dcterms:bibliographicCitation>First publ. in: Dalton Transactions (2003), 11, pp. 2342-2352</dcterms:bibliographicCitation>
    <dc:contributor>Zális, Stanislav</dc:contributor>
    <dcterms:title>Aminoallenylidene complexes of ruthenium(II) from the regioselective addition of secondary amines to butatrienylidene intermediates: a combined experimental and theoretical study of the hindered rotation around the CN-bond</dcterms:title>
    <dc:contributor>Hartmann, Stephan</dc:contributor>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/13835/1/winter_etal.pdf"/>
    <dc:contributor>Klinkhammer, Karl Wilhelm</dc:contributor>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:creator>Zális, Stanislav</dc:creator>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-27T12:36:28Z</dcterms:available>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dcterms:issued>2003</dcterms:issued>
  </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
Supplemental material: http://www.rsc.org/suppdata/dt/b2/b211774f/
Allianzlizenz
Corresponding Authors der Uni Konstanz vorhanden
Internationale Co-Autor:innen
Universitätsbibliographie
Nein
Begutachtet
Diese Publikation teilen