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Oxygen‐Promoted CH Bond Activation at Palladium |
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| Authors: | Dr. Margaret L. Scheuermann David W. Boyce Prof. Kyle A. Grice Prof. Werner Kaminsky Prof. Stefan Stoll Prof. William B. Tolman Prof. Ole Swang Prof. Karen I. Goldberg |
| Affiliation: | 1. Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195 (USA);2. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455 (USA);3. Present address: Department of Chemistry, DePaul University, 1110 West Belden Avenue, Chicago, IL 60614 (USA);4. inGAP Centre for Research‐Based Innovation, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315 Oslo (Norway);5. SINTEF Materials and Chemistry, P.O. Box 124, Blindern, 0314 Oslo (Norway) |
| Abstract: | [Pd(P(Ar)(tBu)2)2] ( 1 , Ar=naphthyl) reacts with molecular oxygen to form PdII hydroxide dimers in which the naphthyl ring is cyclometalated and one equivalent of phosphine per palladium atom is released. This reaction involves the cleavage of both C? H and O? O bonds, two transformations central to catalytic aerobic oxidizations of hydrocarbons. Observations at low temperature suggest the initial formation of a superoxo complex, which then generates a peroxo complex prior to the C? H activation step. A transition state for energetically viable C? H activation across a Pd? peroxo bond was located computationally. |
| Keywords: | C H activation hydroxylation palladium peroxo superoxo |