Peroxymetalation, pseudocyclic

The pseudocyclic peroxymetalation process (outer half-circle of Scheme 3) involves the protonated hydroperoxo intermediate (70b) as the reactive intermediate and appears more likely... 

Strukul and co workers recently prepared a series of cis and trans isomers of the platinum- (-butyl peroxide complexes Pt(R)(OOBu )L2 (R = CF3, Ph, etc. L = tertiary phosphine). The X-ray crystal structure of the (ranx-[Pt(Ph)(OOBu )(PPh3)2] (88) revealed a square-planar arrangement with end-bonded OOBu group. Interestingly, only the trans isomers were found to be capable of oxidizing terminal alkenes to methyl ketones, whereas the cis isomers were inactive. The suggested mechanism involves the coordination of the alkene leading to a five-coordinate intermediate, followed by a pseudocyclic peroxymetalation, as in Scheme 6 (equation 92). ... 

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