Halide-promoted dioxygenolysis of a carbon-carbon bond by a copper(II) diketonate complex

Caleb J. Allpress, Anna Miłaczewska, Tomasz Borowski, Jami R. Bennett, David L. Tierney, Atta M. Arif, Lisa M. Berreau

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Abstract

A mononuclear Cu(II) chlorodiketonate complex was prepared, characterized, and found to undergo oxidative aliphatic carbon-carbon bond cleavage within the diketonate unit upon exposure to O2 at ambient temperature. Mechanistic studies provide evidence for a dioxygenase-type C-C bond cleavage reaction pathway involving trione and hypochlorite intermediates. Significantly, the presence of a catalytic amount of chloride ion accelerates the oxygen activation step via the formation of a Cu-Cl species, which facilitates monodentate diketonate formation and lowers the barrier for O2 activation. The observed reactivity and chloride catalysis is relevant to Cu(II) halide-catalyzed reactions in which diketonates are oxidatively cleaved using O2 as the terminal oxidant. The results of this study suggest that anion coordination can play a significant role in influencing copper-mediated oxygen activation in such systems.

Original languageEnglish (US)
Pages (from-to)7821-7824
Number of pages4
JournalJournal of the American Chemical Society
Volume136
Issue number22
DOIs
StatePublished - Jun 4 2014

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    Allpress, C. J., Miłaczewska, A., Borowski, T., Bennett, J. R., Tierney, D. L., Arif, A. M., & Berreau, L. M. (2014). Halide-promoted dioxygenolysis of a carbon-carbon bond by a copper(II) diketonate complex. Journal of the American Chemical Society, 136(22), 7821-7824. https://doi.org/10.1021/ja502577b