Bimetallic Pd(III) complexes in palladium-catalysed carbon-heteroatom bond formation

被引:507
作者
Powers, David C. [1 ]
Ritter, Tobias [1 ]
机构
[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA
关键词
REDUCTIVE ELIMINATION; OXIDATIVE FUNCTIONALIZATION; PLATINUM(II) COMPLEXES; ARYL HALIDES; SCOPE; THERMODYNAMICS; SUBSTITUTION; HALOGENATION; FLUORINATION; REACTIVITY;
D O I
10.1038/NCHEM.246
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Palladium is a common transition metal for catalysis, and the fundamental organometallic reactivity of palladium in its O, I, II and IV oxidation states is well established. The potential role of Pd(III) in catalysis has not been investigated because organometallic reactions that involve Pd(III) have not been reported previously. In this article we present the formation of carbon-heteroatom bonds from discrete bimetallic Pd(III) complexes and show the synergistic involvement of two palladium atoms of the bimetallic core during both oxidation and reductive elimination. Our results challenge the currently accepted mechanism for oxidative palladium catalysis via Pd(II)-Pd(IV) redox cycles and implicate bimetallic palladium complexes in redox catalysis. The new mechanistic insight provides an opportunity to explore rationally the potential of bimetallic palladium catalysis for synthesis.
引用
收藏
页码:302 / 309
页数:8
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