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

doi:10.1021/ja502577b

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

Chemistry (Twin Cities)

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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 language	English (US)
Pages (from-to)	7821-7824
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	22
DOIs	https://doi.org/10.1021/ja502577b
State	Published - Jun 4 2014

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title = "Halide-promoted dioxygenolysis of a carbon-carbon bond by a copper(II) diketonate complex",

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.",

author = "Allpress, {Caleb J.} and Anna Mi{\l}aczewska and Tomasz Borowski and Bennett, {Jami R.} and Tierney, {David L.} and Arif, {Atta M.} and Berreau, {Lisa M.}",

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T1 - Halide-promoted dioxygenolysis of a carbon-carbon bond by a copper(II) diketonate complex

AU - Allpress, Caleb J.

AU - Miłaczewska, Anna

AU - Borowski, Tomasz

AU - Bennett, Jami R.

AU - Tierney, David L.

AU - Arif, Atta M.

AU - Berreau, Lisa M.

PY - 2014/6/4

Y1 - 2014/6/4

N2 - 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.

AB - 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.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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ER -

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

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