Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States

Lade...
Vorschaubild
Dateien
Zu diesem Dokument gibt es keine Dateien.
Datum
2012
Autor:innen
Hervault, Yves-Marie
Norel, Lucie
Rigaut, Stephane
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
Core Facility der Universität Konstanz
Gesperrt bis
Titel in einer weiteren Sprache
Forschungsvorhaben
Organisationseinheiten
Zeitschriftenheft
Publikationstyp
Zeitschriftenartikel
Publikationsstatus
Published
Erschienen in
Zusammenfassung

Triruthenium (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)}(2) (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl)ruthenium precursors (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡CR'} (2a,b: R' = TMS; 3a,b: R' = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)(2)Ru}(2){μ-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡C} (A(a), R = H; A(b), R = OMe) and {RuCl(CO)(P(i)Pr(3))(2)}(2){μ-CH═CH-1,4-C(6)H(2)-2,5-R(2)-CH═CH} (V(a), R = H; V(b), R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)(2)Ru-C≡C-1,4-C(6)H(4)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)] (M(a)). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use (13)CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,b(n+) (n = 0-3), A(a,b)(n+) and V(a,b)(n+) (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.

Zusammenfassung in einer weiteren Sprache
Fachgebiet (DDC)
540 Chemie
Schlagwörter
Konferenz
Rezension
undefined / . - undefined, undefined
Zitieren
ISO 690WUTTKE, Evelyn, Florian PEVNY, Yves-Marie HERVAULT, Lucie NOREL, Malte DRESCHER, Rainer F. WINTER, Stephane RIGAUT, 2012. Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States. In: Inorganic Chemistry. 2012, 51(3), pp. 1902-1915. ISSN 0020-1669. eISSN 1520-510X. Available under: doi: 10.1021/ic2022177
BibTex
@article{Wuttke2012-02-06Fully-20627,
  year={2012},
  doi={10.1021/ic2022177},
  title={Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States},
  number={3},
  volume={51},
  issn={0020-1669},
  journal={Inorganic Chemistry},
  pages={1902--1915},
  author={Wuttke, Evelyn and Pevny, Florian and Hervault, Yves-Marie and Norel, Lucie and Drescher, Malte and Winter, Rainer F. and Rigaut, Stephane}
}
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/123456789/20627">
    <dcterms:issued>2012-02-06</dcterms:issued>
    <dcterms:title>Fully Delocalized (Ethynyl)(vinyl)phenylene Bridged Triruthenium Complexes in up to Five Different Oxidation States</dcterms:title>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/52"/>
    <dc:creator>Hervault, Yves-Marie</dc:creator>
    <dc:contributor>Winter, Rainer F.</dc:contributor>
    <dc:rights>terms-of-use</dc:rights>
    <dc:creator>Winter, Rainer F.</dc:creator>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2012-11-08T09:02:39Z</dc:date>
    <dc:creator>Rigaut, Stephane</dc:creator>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:language>eng</dc:language>
    <dc:creator>Norel, Lucie</dc:creator>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2012-11-08T09:02:39Z</dcterms:available>
    <dc:contributor>Hervault, Yves-Marie</dc:contributor>
    <dc:creator>Drescher, Malte</dc:creator>
    <dc:contributor>Wuttke, Evelyn</dc:contributor>
    <dcterms:bibliographicCitation>Inorganic chemistry ; 51 (2012), 3. - S. 1902–1915</dcterms:bibliographicCitation>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dc:creator>Pevny, Florian</dc:creator>
    <dc:contributor>Pevny, Florian</dc:contributor>
    <dc:creator>Wuttke, Evelyn</dc:creator>
    <dc:contributor>Rigaut, Stephane</dc:contributor>
    <dcterms:abstract>Triruthenium [(dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)}(2)](n+) (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl)ruthenium precursors (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡CR'} (2a,b: R' = TMS; 3a,b: R' = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)(2)Ru}(2){μ-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡C} (A(a), R = H; A(b), R = OMe) and {RuCl(CO)(P(i)Pr(3))(2)}(2){μ-CH═CH-1,4-C(6)H(2)-2,5-R(2)-CH═CH} (V(a), R = H; V(b), R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)(2)Ru-C≡C-1,4-C(6)H(4)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)] (M(a)). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use (13)CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,b(n+) (n = 0-3), A(a,b)(n+) and V(a,b)(n+) (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.</dcterms:abstract>
    <dc:contributor>Drescher, Malte</dc:contributor>
    <dc:contributor>Norel, Lucie</dc:contributor>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/20627"/>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/52"/>
    <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