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Issue 88, 2013
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Radical Pd(III)/Pd(I) reductive elimination in palladium sequences

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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

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The article was received on 19 Aug 2013, accepted on 15 Sep 2013 and first published on 17 Sep 2013

Article type: Communication
DOI: 10.1039/C3CC46355A
Citation: Chem. Commun., 2013,49, 10424-10426
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    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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