Cutting Peroxides Without Oxidation

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Science  06 Dec 2002:
Vol. 298, Issue 5600, pp. 1851
DOI: 10.1126/science.298.5600.1851a

The binding of organic peroxides to metal centers occurs naturally as well as in industrial processes. Subsequent reactions often break the O-O bond in oxidation processes that can be “heteroleptic” (creating two ions) or “homoleptic” (spliting the electrons of the bond evenly to create two radicals). DiPasquale et al. report on a Ti(IV) complex (1), Cp2Ti(OOtBu)Cl (where Cp is η5-C5H5 and tBu is tert-butyl) that reacts with triethylphosphine (PEt3) to form the phosphinite Et2POtBu in near-quantitative yield. The authors argue for a mechanism in which the O-O bond undergoes homolysis so that the ·OtBu group reacts with PEt3 to form the product and an ethyl radical. Homolysis is supported by the finding of a positive activation entropy. The other product, Cp2Ti(O·)Cl, is unexpectedly stable and does not go on to oxidize PEt3 to Et3PO. — PDS

J. Am. Chem. Soc. 10.1021/ja028500a (2002).

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