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![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Reaction of O2 with [(-)-sparteine]Pd(H)Cl: evidence for an intramolecular [H-L]+ "reductive elimination" pathway
Nattawan Decharin1, Brian V Popp, Shannon S Stahl
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Abstract:
(Sp)PdCl(2) [Sp = (-)-sparteine] catalyzes a number of different aerobic oxidation reactions, and reaction of O(2) with a Pd(II)-hydride intermediate, (Sp)Pd(H)Cl (1), is a key step in the proposed catalytic mechanism. Previous computational studies suggest that O(2) inserts into the Pd(II)-H bond, initiated by abstraction of the hydrogen atom by O(2). Experimental and computational results obtained in the present study challenge this conclusion. Oxygenation of in-situ-generated (Sp)Pd(H)Cl exhibits a zero-order dependence on [O(2)]. This result is inconsistent with a bimolecular H-atom-abstraction pathway, and DFT computational studies identify a novel "reductive elimination" mechanism, in which the chelating nitrogen ligand undergoes intramolecular deprotonation of the Pd(II)-hydride. The relevance of this mechanism to other Pd(II) oxidation catalysts with chelating nitrogen ligands is evaluated.
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