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Concerning the electronic coupling of MoMo quadruple bonds linked by 4,4′-azodibenzoate and comparison with t-Ru(II) centers by 4,4′-azodiphenylcyanamido ligands

Inorganic Chemistry, ISSN: 0020-1669, Vol: 45, Issue: 26, Page: 11035-11042
2006
  • 16
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Metrics Details

  • Citations
    16
    • Citation Indexes
      16
  • Captures
    20

Article Description

From the reactions between Mo(OC Bu) and each of terephthalic acid and 4,4′-azodibenzoic acid, the compounds [Mo(OC Bu)](μ-OCCH CO) (1) and [Mo(OC Bu)](μ-OCCH NCHCO) (2) have been made and characterized by spectroscopic and electrochemical methods. Their electronic structures have been examined by computations employing density functional theory on model compounds where HCO substitutes for BuCO. On the basis of these studies, the two Mo units are shown to be only weakly coupled and the mixed-valence ions 1 and 2 to be valence-trapped and Class II and I, respectively, on the Robin-Day classification scheme for mixed-valence compounds. These results are compared to t-Ru centers linked by 1,4-dicyanamidobenzene and azo-4,4′-diphenylcyanamido bridges for which the mixed-valence ions [Ru-bridge-Ru] have been previously classified as fully delocalized, Class III [Crutchley et al. Inorg. Chem. 2001, 40, 1189; Inorg. Chem. 2004, 43, 1770], and on the basis of results described herein, it is proposed that the latter complex ion is more likely a mixed-valence organic radical where the bridge is oxidized and not the Ru(2+) centers. © 2006 American Chemical Society.

Bibliographic Details

Malcolm H. Chisholm; Jason S. D'Acchioli; Christopher M. Hadad; Nathan J. Patmore

American Chemical Society (ACS)

Chemistry

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