Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

Abdel-Rahman, Obadah S.; Maurer, Jörg; Záliš, Stanislav; Winter, Rainer F.

Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

Dateien

Zu diesem Dokument gibt es keine Dateien.

Datum

2015

Autor:innen

Abdel-Rahman, Obadah S.

Maurer, Jörg

Záliš, Stanislav

Winter, Rainer F.

DOI (zitierfähiger Link)

https://doi.org/10.1021/acs.organomet.5b00401

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

unikn.publication.listelement.citation.prefix.version.undefined

Organometallics. 2015, 34(14), pp. 3611-3628. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.5b00401

Zusammenfassung

A series of ruthenium styryl complexes with potentially noninnocent κ2[N,O]− or κ2[N,S]− ligands have been prepared by treatment of 5-coordinated 16-valence-electron ruthenium styryl complexes Ru(CO)Cl(PiPr3)2(CH═CH-C6H4-4R) with deprotonated bidentate 2-hydroxy- or 2-mercaptopyridines or 2-hydroxy- or 2-mercaptoquinolines. These 6-coordinated complexes have been characterized by NMR and IR spectroscopy and by cyclic voltammetry. Moreover, the structures of complexes 1d, 2a, 3c, 5b, and 6b have been established by X-ray crystallography. Our results indicate that the pyridine-derived complexes exist as two isomers that differ with respect to the orientation of the κ2[N,O]− or κ2[N,S]− donor ligands relative to the CO and alkenyl ligands in the equatorial plane. The equilibrium between the two isomers is thermodynamically controlled. Thus, the relative amount of the minor isomer increases at higher temperatures. With the 2-hydroxyquinoline- or 2-mercaptoquinoline-derived ligands only one isomer is observed. Electrochemical studies show that these complexes undergo one or two reversible consecutive one-electron oxidations, the potentials of which respond to the electronic properties of the 4-substituent at the styryl ligand and those of the ancillary chelate ligand. Strong ligand contributions to the first oxidation of the complexes were experimentally verified by IR and EPR spectroelectrochemistry. Quantum chemical calculations reproduce our experimental results, including the positions of the Ru(CO) vibrational bands of the neutral complexes and of their corresponding radical cations. Our combined results indicate that the oxidation of all complexes is dominated by the styryl ligand, irrespective of the electronic nature of the 4-substituent and of the [N,O]− or [N,S]− chelate ligand.

Fachgebiet (DDC)

540 Chemie

Zitieren

ISO 690

ABDEL-RAHMAN, Obadah S., Jörg MAURER, Stanislav ZÁLIŠ, Rainer F. WINTER, 2015. Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline. In: Organometallics. 2015, 34(14), pp. 3611-3628. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/acs.organomet.5b00401

BibTex

@article{AbdelRahman2015-07-27Ruthe-31998,
  year={2015},
  doi={10.1021/acs.organomet.5b00401},
  title={Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline},
  number={14},
  volume={34},
  issn={0276-7333},
  journal={Organometallics},
  pages={3611--3628},
  author={Abdel-Rahman, Obadah S. and Maurer, Jörg and Záliš, Stanislav and Winter, Rainer F.}
}

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/123456789/31998">
    <dc:contributor>Maurer, Jörg</dc:contributor>
    <dc:language>eng</dc:language>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dc:creator>Abdel-Rahman, Obadah S.</dc:creator>
    <dcterms:issued>2015-07-27</dcterms:issued>
    <dcterms:abstract xml:lang="eng">A series of ruthenium styryl complexes with potentially noninnocent κ2[N,O]− or κ2[N,S]− ligands have been prepared by treatment of 5-coordinated 16-valence-electron ruthenium styryl complexes Ru(CO)Cl(PiPr3)2(CH═CH-C6H4-4R) with deprotonated bidentate 2-hydroxy- or 2-mercaptopyridines or 2-hydroxy- or 2-mercaptoquinolines. These 6-coordinated complexes have been characterized by NMR and IR spectroscopy and by cyclic voltammetry. Moreover, the structures of complexes 1d, 2a, 3c, 5b, and 6b have been established by X-ray crystallography. Our results indicate that the pyridine-derived complexes exist as two isomers that differ with respect to the orientation of the κ2[N,O]− or κ2[N,S]− donor ligands relative to the CO and alkenyl ligands in the equatorial plane. The equilibrium between the two isomers is thermodynamically controlled. Thus, the relative amount of the minor isomer increases at higher temperatures. With the 2-hydroxyquinoline- or 2-mercaptoquinoline-derived ligands only one isomer is observed. Electrochemical studies show that these complexes undergo one or two reversible consecutive one-electron oxidations, the potentials of which respond to the electronic properties of the 4-substituent at the styryl ligand and those of the ancillary chelate ligand. Strong ligand contributions to the first oxidation of the complexes were experimentally verified by IR and EPR spectroelectrochemistry. Quantum chemical calculations reproduce our experimental results, including the positions of the Ru(CO) vibrational bands of the neutral complexes and of their corresponding radical cations. Our combined results indicate that the oxidation of all complexes is dominated by the styryl ligand, irrespective of the electronic nature of the 4-substituent and of the [N,O]− or [N,S]− chelate ligand.</dcterms:abstract>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:creator>Maurer, Jörg</dc:creator>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/31998"/>
    <dcterms:title>Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline</dcterms:title>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:contributor>Záliš, Stanislav</dc:contributor>
    <dc:contributor>Winter, Rainer F.</dc:contributor>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2015-10-27T14:54:21Z</dc:date>
    <dc:contributor>Abdel-Rahman, Obadah S.</dc:contributor>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:creator>Záliš, Stanislav</dc:creator>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2015-10-27T14:54:21Z</dcterms:available>
    <dc:creator>Winter, Rainer F.</dc:creator>
  </rdf:Description>
</rdf:RDF>

Universitätsbibliographie

Ja