title: Copper/alpha-ketocarboxylate chemistry with supporting peralkylated diamines: reactivity of copper(I) complexes and dicopper-oxygen intermediates.
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.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, USA.
authors.forename: Aalo K
authors.initials: AK
authors.lastname: Gupta
authors.forename: William B
authors.initials: WB
authors.lastname: Tolman
mesh_terms: D002264:Carboxylic Acids / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003959:Diamines / Q000737:chemistry; D005029:Ethylenediamines / Q000737:chemistry; D006038:Glyoxylates / Q000737:chemistry; D008024:Ligands; D008333:Mandelic Acids / Q000737:chemistry; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D003959:Diamines; D005029:Ethylenediamines; D006038:Glyoxylates; D008024:Ligands; D008333:Mandelic Acids; C027450:dimethylethylenediamine; C012482:phenylglyoxylic acid; D003300:Copper; D010100:Oxygen