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Insertion of molecular oxygen into a palladium(II) hydride bond
Melanie C Denney1, Nicole A Smythe, Kara L Cetto
1Department of Chemistry, University of Washington, Seattle, 98195-1700, USA.
Abstract:
Insertion of molecular oxygen into a palladium(II) hydride bond to form an (eta1-hydroperoxo)palladium(II) complex is reported. The hydroperoxo palladium(II) product has been crystallographically characterized. A second-order rate law (first-order in palladium and first-order in oxygen) is observed for the reaction and a large kinetic isotope effect implicates Pd-H bond cleavage in the rate-determining step. The results of studies with radical inhibitors and light suggest that the reaction does not proceed by a radical chain mechanism.
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