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Studies on Transition Metal Peroxo Complexes. Part 8. The Nature of Peroxomolybdates and Peroxotungstates in Aqueous Solution

DOI: 10.1039/DT9890001203

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1203 - 1208 (1989)

Update date:2022-08-10

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Authors:

Campbell, Nicholas J.Campbell, Nicholas J.

Dengel, Andrew C.Dengel, Andrew C.

Edwards, Catherine J.Edwards, Catherine J.

Griffith, William P.Griffith, William P.

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Article abstract of DOI:10.1039/DT9890001203

The nature of the species formed in solutions of (2-) and (2-) (1-0.1 mol dm-3) in the presence of H2O2 (5-0.5 mol dm-3) from pH 12 to acid has been studied by Raman and i.r. spectroscopy and, for molybdenum-containing species, by (95)Mo n.m.r. spectroscopy.The polymerisation processes are far less complex in the presence of H2O2 than in its absence.The principal species are likely to be (2-), (2-), (2-) and, at lower pH, complexes containing the (2+) unit.Vibrational assignments are proposed for K2*2H2O (M = Mo or W) using (18)O and (2)H substitution.Parallel studies on the oxidation of alcohols and alkenes by (2-) in excess of H2O2 from pH 7 to 0.5 suggest that (2-) is the most effective oxidising species.Stoicheiometric oxidations of primary alcohols to aldehydes, of secondary alcohols to ketones, and of cyclohexene to its epoxide by 2 are briefly reported.

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