Catalysis using palladium generally occurs through two-electron processes, and myriad useful transformations have been developed under this manifold. As a point of contrast, it is frequently challenging to control whether first row transition metals operate through two- or one-electron  mechanisms. In this context, we have discovered that organopalladium(II) species that are catalytically relevant to modern coupling reactions can be triggered to switch to a one-electron reaction manifold by direct visible light excitation leading to mild homolysis of the organometallic bond at room temperature. Such a process with other organopalladium complexes historically has required UV light and/or occurred in structures with less relevance to typical catalytic applications. Spectroscopic and computational data to understand the photophysical process that drives the liberation of alkyl radicals from these complexes will be discussed. Preliminary experiments also suggest simple palladium(II) species have potential to exploit such one-electron reactivity under visible light irradiation to enable new organic transformations.

Visible light photocleavage of metal-carbon bonds in organopalladium complexes

2019 Spring National Meeting

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