Palladium(II)-catalyzed oxidation reactions are an important class of methods for selective modification of organic molecules. Ancillary ligands have greatly improved the synthetic utility of these reactions, yet in many cases their influences are poorly understood. In particular, the influence of catalytically relevant ancillary ligands on PdII/0 redox potentials has not been documented. This talk will present the discovery of (L)PdII(OAc)2-mediated oxidation of hydroquinones (L = bathocuproine, 4,5-diazafluoren-9-one), generating an equilibrium mixture of (L)PdII(OAc)2 and reduced (L)Pd species. Analysis of the redox equilibria provides the basis for determination of (L)PdII(OAc)2 reduction potentials. Complementary density functional theory calculations demonstrate that minor structural modifications to nitrogen-based ligands can modulate the (L)PdII(OAc)2 reduction potential by 375 mV.

Using ancillary ligands to modulate palladium(II) redox potentials

ACS Spring Meeting 2021

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