Halide-Promoted Dioxygenolysis of a Carbon-Carbon Bond by a Copper(II) Diketonate Complex

被引：29

作者：

Allpress, Caleb J. ^{[1
]}

Milaczewska, Anna ^{[2
]}

Borowski, Tomasz ^{[2
]}

Bennett, Jami R. ^{[3
]}

Tierney, David L. ^{[3
]}

Arif, Atta M. ^{[4
]}

Berreau, Lisa M. ^{[1
]}

机构：

[1] Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA

[2] Polish Acad Sci, Jerzy Haber Inst Catalysis & Surface Chem, PL-30239 Krakow, Poland

[3] Miami Univ, Dept Chem & Biochem, Oxford, OH 45056 USA

[4] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 22期

基金：

美国国家科学基金会;

关键词：

OXIDATIVE CLEAVAGE; CHEMISTRY; CRYSTAL; SPECTRA; KETONES;

D O I：

10.1021/ja502577b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 O-2 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 O-2 activation. The observed reactivity and chloride catalysis is relevant to Cu(II) halide-catalyzed reactions in which diketonates are oxidatively cleaved using O-2 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.

引用

页码：7821 / 7824

页数：4

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