双核 Pd(III)配合物的双金属还原消除。
Bimetallic reductive elimination from dinuclear Pd(III) complexes.
机构信息
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA.
出版信息
J Am Chem Soc. 2010 Oct 13;132(40):14092-103. doi: 10.1021/ja1036644.
Abstract
In 2009, we reported C-halogen reductive elimination reactions from dinuclear Pd(III) complexes and implicated dinuclear intermediates in Pd(OAc)(2)-catalyzed C-H oxidation chemistry. Herein, we report results of a thorough experimental and theoretical investigation of the mechanism of reductive elimination from such dinuclear Pd(III) complexes, which establish the role of each metal during reductive elimination. Our results implicate reductive elimination from a complex in which the dinuclear core is intact and suggest that redox synergy between the two metals is responsible for the facile reductive elimination reactions observed.
摘要
2009 年，我们报道了双核 Pd(III)配合物的 C-卤化物还原消除反应，并在 Pd(OAc)2 催化的 C-H 氧化反应中提出双核中间体。在此，我们报告了对这种双核 Pd(III)配合物还原消除反应机理的全面实验和理论研究结果，该结果确定了每个金属在还原消除过程中的作用。我们的结果表明，还原消除是从双核核完整的配合物中发生的，并表明两个金属之间的氧化还原协同作用是导致观察到的容易还原消除反应的原因。
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