Transition Metal Chemistry

, Volume 37, Issue 6, pp 505–517 | Cite as

Mechanistic studies of the selective reduction of ruthenium(III) containing trinuclear oxo complexes by l-ascorbic acid in aqueous solution

  • Mark A. W. Lawrence
  • Paul T. Maragh
  • Tara P. Dasgupta


The reduction of the Ru(III) oxo-centred trinuclear acetate cations, [Ru33-O)(μ2-CH3CO2)6(H2O)3]+ and [Ru2Cr(μ3-O)(μ2-CH3CO2)6(H2O)3]+, by the biological reductant l-ascorbic acid was studied spectrophotometrically under pseudo first-order conditions over the ranges 3.05 ≤ pH ≤ 4.83 (acetate buffer), 15 °C ≤ θ ≤ 30 °C and at I = 0.5 mol dm−3 (NaClO4). The first electron transfer in the redox process resulted in mixed-valence species [Ru2M(μ3-O)(μ2-CH3CO2)6(H2O)3]0, where M = Ru or Cr, followed by the slow consecutive reduction of other Ru(III) ions. The kinetics of the formation of the mixed-valence species was studied in detail, and a mechanism in support of these data is proposed. The intricate mechanistic details of the subsequent reactions are unclear as the spectral characteristics of the species involved could not be resolved from those of the first intermediate. The final products, however, were found to be Ru(II) (and Cr(III) for the mixed-metal species) in acetate buffer. The electron-transfer mechanism has been proposed to be inner-sphere, as deduced from Marcus cross-relationship. In an aqueous acetate buffer at I = 1.0 mol dm−3 (NaClO4), the cyclic voltammograms of the complexes were found to be quasi-reversible and pH dependent and have values of 0.18 and 0.19 V (relative to SHE) at pH = 3.41 for the [Ru33-O)(μ2-CH3CO2)6(H2O)3]+ and [Ru2Cr(μ3-O)(μ2-CH3CO2)6(H2O)3]+ cations, respectively.


Ruthenium Complex Cation Observe Rate Constant 8453A Diode Array Spectrophotometer Predict Rate Constant 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors would like to thank Professor Willem H. Mulder and Ms Kerry-Ann Green for their valuable comments to this work, and The University of the West Indies (Mona) Board of Graduate Studies and Research, for funding.

Supplementary material

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Supplementary material 1 (DOC 517 kb)
11243_2012_9616_MOESM2_ESM.doc (26 kb)
Supplementary material 2 (DOC 26 kb)
11243_2012_9616_MOESM3_ESM.doc (36 kb)
Supplementary material 3 (DOC 36 kb)


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Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Mark A. W. Lawrence
    • 1
  • Paul T. Maragh
    • 1
  • Tara P. Dasgupta
    • 1
  1. 1.Department of ChemistryUniversity of the West IndiesJamaicaWest Indies

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