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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
Copper/alpha-ketocarboxylate chemistry with supporting peralkylated diamines: reactivity of copper(I) complexes and
Aalo K Gupta1, William B Tolman
1Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, USA.
Abstract:
To further understand copper-promoted oxidation reactions, the Cu(I) complexes LCuX (L = N,N'-di-tert-butyl-N,N'-dimethylethylenediamine; X = benzoylformate (BF) or p-nitro-benzoylformate) were synthesized, fully characterized by X-ray crystallography and spectroscopy in solution, and their reactivity with O(2) at -80 degrees C examined. Oxidative decarboxylation of the alpha-ketocarboxylate ligand was observed, but only to a significant extent when cyclohexene, cyclooctene, or acetonitrile was present. Spectroscopic and conductivity data are consistent with mechanistic postulates involving displacement of the alpha-ketocarboxylate by the additives to a small extent, followed by oxygenation of the LCu(I) moiety to yield copper-oxygen species that subsequently induce decarboxylation. To test these hypotheses, spectroscopic and kinetic studies of the reactions of Bu(4)NBF with preformed mu-eta(2):eta(2)-peroxodicopper(II) and/or bis(mu-oxo)dicopper(III) complexes supported by L or N,N,N',N'-tetramethylpropylenediamine were performed. In an illustration of a new mode of reactivity for such dicopper-oxygen cores, decarboxylation of the added alpha-ketocarboxylate was observed and the intermediacy of a carboxylate-bridged mu-eta(2):eta(2)-peroxodicopper(II) complex was implicated.
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