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. 2006 Mar 1;128(8):2508-9.
doi: 10.1021/ja0562292.

Insertion of molecular oxygen into a palladium(II) hydride bond

Melanie C Denney  1 , Nicole A Smythe, Kara L Cetto, Richard A Kemp, Karen I Goldberg
Affiliations

Insertion of molecular oxygen into a palladium(II) hydride bond

Melanie C Denney et al. J Am Chem Soc. .

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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