Article abstract
Nature Chemistry 1, 302 - 309 (2009)
Published online: 7 June 2009 | Corrected online: 24 June 2009 | doi:10.1038/nchem.246
There is a Corrigendum (September 2009) associated with this Article.
Subject Categories: Catalysis | Organometallic chemistry
Bimetallic Pd(III) complexes in palladium-catalysed carbon–heteroatom bond formation
David C. Powers1 & Tobias Ritter1
Abstract
Palladium is a common transition metal for catalysis, and the fundamental organometallic reactivity of palladium in its 0, 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.
- Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts, USA
Correspondence to: Tobias Ritter1 e-mail: ritter@chemistry.harvard.edu
S‡) = -11.2 
9.4 cal
K-1; (2) page 305, top of column 2 should read: (G‡298 = 20.3 0.1 kcal mol-1, H‡ = 23.4 3.4 kcal mol-1, and S‡ = 10.2 11.4 cal K-1). The authors wish to confirm that the corrections have no implications for their conclusions or the mechanistic proposal they have put forward. These changes have now been corrected on the HTML and PDF versions of this article.