@article{Maurer2008-01-09Ruthe-13826,
  year={2008},
  doi={10.1021/ja075547t},
  title={Ruthenium Complexes with Vinyl, Styryl, and Vinylpyrenyl Ligands: A Case of Non-innocence in Organometallic Chemistry},
  number={1},
  volume={130},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={259--268},
  author={Maurer, Jörg and Linseis, Michael and Sarkar, Biprajit and Schwederski, Brigitte and Niemeyer, Mark and Kaim, Wolfgang and Zális, Stanislav and Anson, Chris and Zabel, Manfred and Winter, Rainer F.}
}

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    <dc:contributor>Niemeyer, Mark</dc:contributor>
    <dc:contributor>Linseis, Michael</dc:contributor>
    <dc:creator>Kaim, Wolfgang</dc:creator>
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    <dc:language>eng</dc:language>
    <dc:contributor>Maurer, Jörg</dc:contributor>
    <dc:contributor>Anson, Chris</dc:contributor>
    <dcterms:issued>2008-01-09</dcterms:issued>
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    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-23T19:44:16Z</dc:date>
    <dc:creator>Maurer, Jörg</dc:creator>
    <dc:contributor>Zális, Stanislav</dc:contributor>
    <dc:creator>Anson, Chris</dc:creator>
    <dcterms:bibliographicCitation>First publ. in: Journal of the American Chemical Society 130 (2008), 1, pp. 259-268</dcterms:bibliographicCitation>
    <dcterms:abstract xml:lang="eng">We herein describe a systematic account of mononuclear ruthenium vinyl complexes L−{Ru}−CHCH−R where the phosphine ligands at the (PR‘3)2Ru(CO)Cl{Ru} moiety, the coordination number at the metal (L = 4-ethylisonicotinate or a vacant coordination site) and the substituent R (R = nbutyl, phenyl, 1-pyrenyl) have been varied. Structures of the enynyl complex Ru(CO)Cl(PPh3)2(η1:η2-nBuHCCHCCnBu), which results from the coupling of the hexenyl ligand of complex 1a with another molecule of 1-hexyne, of the hexenyl complexes (nBuCHCH)Ru(CO)Cl(PiPr3)2 (1c) and (nBuCHCH)Ru(CO)Cl(PPh3)2(NC5H4COOEt-4) (1b), and of the pyrenyl complexes (1-Pyr-CHCH)Ru(CO)Cl(PiPr3)2 (3c) and (1-Pyr-CHCH)Ru(CO)Cl(PPh3)3 (3a-P) have been established by X-ray crystallography. All vinyl complexes undergo a one-electron oxidation at fairly low potentials and a second oxidation at more positive potentials. Anodic half-wave or peak potentials show a progressive shift to lower values as π-conjugation within the vinyl ligand increases. Carbonyl band shifts of the metal-bonded CO ligand upon monooxidation are significantly smaller than is expected of a metal-centered oxidation process and are further diminished as the vinyl CHCH entity is incorporated into a more extended π-system. ESR spectra of the electrogenerated radical cations display negligible g-value anisotropies and small deviations of the average g-value from that of the free electron. The vinyl ligands thus strongly contribute to or even dominate the anodic oxidation processes. This renders them a class of truly “non-innocent” ligands in organometallic ruthenium chemistry. Experimental findings are fully supported by quantum chemical calculations: The contribution of the vinyl ligand to the HOMO increases from 46% (Ru-vinyl delocalized) to 84% (vinyl dominated) as R changes from nbutyl to 1-pyrenyl.</dcterms:abstract>
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    <dc:contributor>Kaim, Wolfgang</dc:contributor>
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    <dc:creator>Sarkar, Biprajit</dc:creator>
    <dc:contributor>Schwederski, Brigitte</dc:contributor>
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    <dc:creator>Niemeyer, Mark</dc:creator>
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    <dc:creator>Linseis, Michael</dc:creator>
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    <dc:creator>Zális, Stanislav</dc:creator>
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