Alkanes vanadium-peroxo complexes

Mimoun, H., L. Saussine, E. Daire, M. Postel, J. Fischer, and R. Weiss. 1983. Vanadium(V) peroxo complexes. New versatile biomimetic reagents for epoxidation of olefins and hydroxylation of alkanes and aromatic hydrocarbons. J. Am. Chem. Soc. 105 3101-3110. 

Vanadium. Vanadyl complexes of the three ligands 14, 24, and 28 were prepared from vanadyl sulfate and the metal-free ligands. They have the expected spectroscopic properties, and this is confirmed by the X-ray crystal structure of the vanadyl complex of 24, which is shown in Fig. 23(a) and has metal-donor bond distances in the expected range. In terms of reactivity, these complexes are rather unspectacular. No haloperoxidase reactivity was observed, and oxidation of alkanes and alkenes is rather sluggish (138). This is not unexpected since with the pentadentate ligands there is no free site at the vanadium(IV) center for metal-substrate interaction. The same is true for the vanadium(V) oxo-peroxo complexes with tetradentate coordination of the pentadentate ligand. 

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