Vanadium(V)-catalyzed oxidation reactions with tert-butyl hydroperoxide (tBuOOH)

INOR 830

Tamás Jakusch, jakusch@umich.edu and Vincent L. Pecoraro, vlpec@umich.edu. Department of Chemistry, University of Michigan, 930 N. University, Ann Arbor, MI 48109
Vanadium dependent haloperoxidases are enzymes capable of oxidizing halides using hydrogen peroxide. Previously, the Pecoraro group developed a set of oxo-peroxo vanadium complexes as functional models for this enzyme class. Protonation of these compounds is essential for the reactivity and is supported by quantum chemical studies showing a decrease in the reaction barrier for oxidation of bromide and thioethers. Successful application of tBuOOH in this reaction could provide experimental evidence of where protonation takes place. The efficacy of tBuOOH for the epoxidation of propylene in the presence of d0 metal complexes is known. Here we report a study on the haloperoxidase and epoxidation activity of a series of tBuOO V(V) complexes.

 

5th International Symposium on Chemistry and Biological Chemistry of Vanadium: Posters in Biochemistry and Chemistry
7:00 PM-10:00 PM, Tuesday, 12 September 2006 Moscone Center -- Hall D, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, 11 September 2006 Moscone Center -- Hall D, Sci-Mix

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006