Palladium Atoms Team Up for Oxidative Additions

  • Author: Chemistry – A European Journal
  • Published Date: 14 February 2018
  • Source / Publisher: Chemistry – A European Journal/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
thumbnail image: Palladium Atoms Team Up for Oxidative Additions

Related Societies

The oxidative addition of organic halides to palladium(0) complexes is a fundamental step in the catalytic cycle of several widely used Pd-catalyzed transformations, such as Suzuki couplings, Heck reactions, and Buchwald-Hartwig aminations. In the case of haloarenes, the textbook mechanism involves the insertion of a single Pd(0) center in the carbon-halogen bond.

Luca Alessandro Perego, École Normale Supérieure and CNRS-Chimie ParisTech, Paris, France, Ilaria Ciofini, CNRS-Chimie ParisTech, Laurence Grimaud, École Normale Supérieure, and colleagues have found that two palladium centers can collaborate in the activation of C–I bonds. Conductimetric monitoring of the reaction of iodoarenes with Pd(0) complexes featuring nitrogen ligands showed a second-order dependence of the reaction rate on the concentration of Pd(0).

Density functional theory (DFT) calculations revealed that one Pd(0) center coordinates the departing iodine atom in a halogen bond-like fashion, while another one inserts in the C–I bond (pictured). This conceptually novel cooperative mechanism could also happen in other systems. According to the researchers, this insight may be exploited to design metal-based catalysts for the activation of less reactive carbon-halogen bonds.


Article Views: 1803

Sign in Area

Please sign in below

Additional Sign In options

Please note that to comment on an article you must be registered and logged in.
Registration is for free, you may already be registered to receive, e.g., the newsletter. When you register on this website, please ensure you view our terms and conditions. All comments are subject to moderation.

Article Comments - To add a comment please sign in

If you would like to reuse any content, in print or online, from, please contact us first for permission. more

Follow on Facebook Follow on Twitter Follow on YouTube Follow on LinkedIn Follow on Instagram RSS Sign up for newsletters

Magazine of Chemistry Europe (16 European Chemical Societies) published by Wiley-VCH