Insertion of molecular oxygen into a palladium(II) hydride bond |
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Authors: | Denney Melanie C Smythe Nicole A Cetto Kara L Kemp Richard A Goldberg Karen I |
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Institution: | Department of Chemistry, University of Washington, Seattle, 98195-1700, USA. |
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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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