Summary
Rate constants are reported for 12-tungstocobaltate(III) [CoW12O40]5− oxidation of iodide in water and in binary aqueous solvent mixtures containing up to 40% methanol, 40% acetonitrile, or 60% dimethyl sulphoxide. From these kinetic results, solubility measurements on potassium 12-tungstocobaltate(III), and published data on Gibbs free energies of transfer of appropriate ions, it has been deduced that the dominant factor in determining the marked decrease in rate observed on going from water into the binary aqueous solvent mixtures is destabilisation of the transition state for the electron-transfer reaction.
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References
M. J. Blandamer and J. Burgess,Pure Appl. Chem., 51, 2087 (1979).
M. J. Blandamer and J. Burgess,Coord. Chem. Rev., 31, 93 (1980).
M. J. Blandamer, J. Burgess, P. P. Duce and R. I. Haines,J. Chem. Soc. Dalton Trans., 2442 (1980).
M. J. Blandamer, J. Burgess, and R. I. Haines,J. Chem. Soc. Chem. Commun., 963 (1978).
L. C. W. Baker and T. P. McCutcheon,J. Am. Chem. Soc., 78, 4503 (1956).
Z. Amjad, J.-C. Brodovitch, and A. McAuley,Can. J. Chem., 55, 3581 (1977).
R. A. Marcus,J. Phys. Chem., 72, 891 (1968); E. Pelizzetti, E. Mentasti, and E. Pramauro,Inorg. Chem., 15, 2898 (1976).
J.-C. Brodovitch, R. I. Haines, A. McAuley and J. Sherwood, unpublished results.
M. J. Blandamer, J. Burgess, S. J. Hamshere, C. White, R. I. Haines and A. McAuley, submitted toCan. J. Chem.
J. Burgess and R. H. Prince,J. Chem. Soc. A, 2111 (1970).
J. Burgess and A. McAuley, (Eds.),Inorganic Reaction Mechanisms, Chem. Soc. Special. Period. Report, London,2, 127 (1972);3, 142 (1974);5, 158 (1977);6, 168 (1979).
D. L. Kepert and J. H. Kyle,J. Chem. Soc. Dalton Trans., 137 (1978).
J. Burgess,J. Chem. Soc. A, 2571 (1968).
J. Burgess,J. Chem. Soc. A, 2351 (1970).
M. J. Blandamer, J. Burgess and A. J. Duffield,J. Chem. Soc. Dalton Trans., 1 (1980); and refs. therein.
C. F. Wells,J. Chem. Soc. Faraday Trans. I, 69, 984 (1973).
C. L. de Ligny and M. Alfenaar,Rec. Trav. Chim., 84, 81 (1965).
B. G. Cox, R. Natarajan and W. E. Waghorne,J. Chem. Soc. Faraday Trans. I, 75, 86 (1979).
B. G. Cox, R. Natarajan and W. E. Waghorne,J. Chem. Soc. Faraday Trans. I, 75, 1780 (1979).
B. G. Cox,Ann. Rep. Chem. Soc., 71A, 249 (1974).
M. T. Beck,Coord. Chem. Rev., 3, 91 (1968).
M. S. Subhani,Rev. Roum. Chim., 23, 719 (1978).
E. Grunwald and S. Winstein,J. Am. Chem. Soc., 70, 846 (1948); P. R. Wells,Linear Free Energy Relationships, Academic Press, London, 1968, chap. 4.
E.g. J. Burgess,J. Chem. Soc. Dalton Trans., 825 (1973); L. A. P. Kane-Maguire and G. Thomas,ibid., 1890 (1975); V. V. Udovenko, L. G. Reiter and I. Beran,Russ. J. Inorg. Chem., 22, 168 (1977).
K. J. Ellis and A. McAuley,J. Chem. Soc. Dalton Trans., 1533 (1973).
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Blandamer, M.J., Burgess, J., Duce, P.P. et al. Initial state and transition state solvation effects in the cobaltitungstate oxidation of iodide in binary aqueous solvent mixtures. Transition Met Chem 7, 10–13 (1982). https://doi.org/10.1007/BF00623798
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DOI: https://doi.org/10.1007/BF00623798