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      New ruthenium carbonyl clusters containing unusual 5-sulfido-, 4-benzyne-, and thianthrene-derived ligands: Insertion of ruthenium into the thianthrene ring by C-S activation

      Hassan, Mohammad R.; Kabir, Shariff E.; Nicholson, Brian K.; Nordlander, Ebbe; Uddin, Md. Nazim
      DOI
       10.1021/om7004707
      Link
       pubs.acs.org.ezproxy.waikato.ac.nz:2048
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      Citation
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      Mohammad R. Hassan, M.R., Kabir, S.E., Nicholson, B.K., Nordlander, E.& Uddin, M.N. (2007). New ruthenium carbonyl clusters containing unusual 5-sulfido-, 4-benzyne-, and thianthrene-derived ligands: Insertion of ruthenium into the thianthrene ring by C-S activation. Organometallics, 26, 4627-4633.
      Permanent Research Commons link: https://hdl.handle.net/10289/226
      Abstract
      Treatment of [Ru3(CO)12] with thianthrene in refluxing toluene afforded [( 4-S)Ru4( -CO)2(CO)9( 4- 2-C6H4)] (1), [( 5-S)Ru6( -CO)2(CO)15( - 3-C12H8S)] (2), and [( 5-S)Ru5( -CO)2(CO)11( - 3-C12H8S)( 4- 2-C6H4)] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4)(MeCN)] (4) in 73% yield. The reaction of 4 with P(OMe)3 gave the substitution product [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4){P(OMe)3}] (5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a 4-capping sulfido and a 4- 2-benzyne ligand, whereas 3, 4, and 5 contain 5-sulfido and 4- 2-benzyne ligands. The latter three compounds provide rare examples of 5-sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the 4- 2-benzyne ligand is perpendicular to the Ru4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne.
      Date
      2007-07-01
      Type
      Journal Article
      Rights
      This article is published in the journal, Organometallics, (c) 2007 American Chemical Society
      Collections
      • Science and Engineering Papers [3086]
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