Ligand-Induced Reductive Elimination of Ethane from Azopyridine Palladium Dimethyl Complexes

Journal of the American Chemical Society
Andrey E RudenkoRobert M Waymouth

Abstract

Reductive elimination (RE) is a critical step in many catalytic processes. The reductive elimination of unsaturated groups (aryl, vinyl and ethynyl) from Pd(II) species is considerably faster than RE of saturated alkyl groups. Pd(II) dimethyl complexes ligated by chelating diimine ligands are stable toward RE unless subjected to a thermal or redox stimulus. Herein, we report the spontaneous RE of ethane from (azpy)PdMe2 complexes and the unique role of the redox-active azopyridine (azpy) ligands in facilitating this reaction. The (azpy)PdMe2 complexes are air- and moisture-stable in the solid form, but they readily produce ethane upon dissolution in polar solvents at temperatures from 10 °C to room temperature without the need for an external oxidant or elevated temperatures. Experimental and computational studies indicate that a bimolecular methyl transfer precedes the reductive elimination step, where both steps are facilitated by the redox-active azopyridine ligand.

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Citations

Dec 10, 2020·The Journal of Chemical Physics·Abel CarrerasDavid Casanova
Feb 11, 2021·The Journal of Physical Chemistry. a·Alan E Rask, Paul M Zimmerman
Jul 8, 2021·Chemical Communications : Chem Comm·Kento NakamuraHiroaki Sasai

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