Issue 88, 2013

Radical Pd(iii)/Pd(i) reductive elimination in palladium sequences

Abstract

Open-shell mechanisms are often at work in catalytic sequences involving first-row transition metals while usually not considered in palladium chemistry. Herein a computational study suggests their possible relevance in catalytic methods involving paramagnetic Pd(III) intermediates. Indeed C–C bond forming reductive elimination previously thought to occur in Pd(IV) complexes has lower barriers in neutral, radical Pd(III) intermediates instead. These species could form upon addition on Pd(II) of an aryl radical generated via single electron transfer from a photo-active ruthenium complex and have the perfect stereoelectronic arrangement to smoothly undergo the coupling process.

Graphical abstract: Radical Pd(iii)/Pd(i) reductive elimination in palladium sequences

Supplementary files

Article information

Article type
Communication
Submitted
19 Aug 2013
Accepted
15 Sep 2013
First published
17 Sep 2013

Chem. Commun., 2013,49, 10424-10426

Radical Pd(III)/Pd(I) reductive elimination in palladium sequences

G. Maestri, M. Malacria and E. Derat, Chem. Commun., 2013, 49, 10424 DOI: 10.1039/C3CC46355A

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