@article{Connelly1999Reduc-13863,
  year={1999},
  doi={10.1021/om990089l},
  title={Reduction of [ML(alkyne)2(η-C5R‘5)]+ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C5R‘5 = C5HPh4): Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes},
  number={16},
  volume={18},
  issn={0276-7333},
  journal={Organometallics},
  pages={3201--3207},
  author={Connelly, Neil and Geiger, William and Lovelace, Sherri and Metz, Bernhard and Paget, Timothy and Winter, Rainer F.}
}

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    <dc:contributor>Connelly, Neil</dc:contributor>
    <dcterms:issued>1999</dcterms:issued>
    <dcterms:title>Reduction of [ML(alkyne)2(η-C5R‘5)]+ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C5R‘5 = C5HPh4): Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes</dcterms:title>
    <dc:contributor>Lovelace, Sherri</dc:contributor>
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    <dc:contributor>Winter, Rainer F.</dc:contributor>
    <dc:creator>Paget, Timothy</dc:creator>
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    <dc:creator>Connelly, Neil</dc:creator>
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    <dc:creator>Geiger, William</dc:creator>
    <dcterms:abstract xml:lang="eng">The complexes [M(NCMe)(RC2R)2(η-C5R‘5)]+ (M = Mo or W, R = Me or Ph; R‘ = H or Me, C5R‘5 = C5HPh4) undergo one-electron reduction to [M(NCMe)(RC2R)2(η-C5R‘5)], which rapidly lose acetonitrile to give the 17-electron complexes [M(RC2R)2(η-C5R‘5)]. The stability of [M(RC2R)2(η-C5R‘5)] depends on R and R‘; for R = Ph, the radical is sufficiently stable so that its reduction to the 18-electron anion [M(RC2R)2(η-C5R‘5)]- is detected in the cyclic voltammogram. Chemical reduction of [Mo(NCMe)(PhC2Ph)2(η-C5HPh4)]+ with [Co(η-C5H5)2] gives the air-sensitive solid [Mo(PhC2Ph)2(η-C5HPh4)], characterized as an alkyne-based radical by ESR spectroscopy, which gives [Mo(NCMe)(PhC2Ph)2(η-C5HPh4)]+ when treated with [Fe(η-C5H5)2]+ in acetonitrile. The carbonyl cations [M(CO)(RC2R)2(η-C5R‘5)]+ (M = Mo, W) undergo two sequential one-electron reductions, the first of which is reversible and gives the 19-electron species [M(CO)(RC2R)2(η-C5R‘5)]. The 19-electron radical [Mo(CO)(PhC2Ph)2(η-C5Me5)] has been characterized in solution by IR and ESR spectroscopy.</dcterms:abstract>
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    <dc:creator>Winter, Rainer F.</dc:creator>
    <dc:contributor>Geiger, William</dc:contributor>
    <dc:contributor>Paget, Timothy</dc:contributor>
    <dc:contributor>Metz, Bernhard</dc:contributor>
    <dcterms:bibliographicCitation>First publ. in: Organometallics 18 (1999), 16, pp. 3201-3207</dcterms:bibliographicCitation>
    <dc:creator>Metz, Bernhard</dc:creator>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-29T09:37:56Z</dc:date>
    <dc:creator>Lovelace, Sherri</dc:creator>
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