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• W2045986609 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 O2 at −80 °C examined. Oxidative decarboxylation of the α-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 α-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 Bu4NBF with preformed μ-η2:η2-peroxodicopper(II) and/or bis(μ-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 α-ketocarboxylate was observed and the intermediacy of a carboxylate-bridged μ-η2:η2-peroxodicopper(II) complex was implicated." @default.
• W2045986609 created "2016-06-24" @default.
• W2045986609 creator A5041102342 @default.
• W2045986609 creator A5086849861 @default.
• W2045986609 date "2010-04-05" @default.
• W2045986609 modified "2023-09-23" @default.
• W2045986609 title "Copper/α-Ketocarboxylate Chemistry With Supporting Peralkylated Diamines: Reactivity of Copper(I) Complexes and Dicopper−Oxygen Intermediates" @default.
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• W2045986609 doi "https://doi.org/10.1021/ic100032n" @default.
• W2045986609 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/2878206" @default.
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