Exploring the Redox Chemistry of Dinuclear Silver Catalysts
In recent years, synthetically useful homogeneous catalysis has been developed with silver, including nitrene transfer reactions for carbon–nitrogen bond formation. However, the mechanisms of silver-catalyzed redox reactions have remained poorly understood, including a near-total lack of experimental data on oxidized intermediates. This talk will discuss our lab’s efforts to better understand the redox chemistry of well-defined silver complexes, with a focus on dinuclear complexes in which silver–silver interactions may play a role in facilitating multi-electron redox processes. First, we will present a detailed experimental study on the reactivity of a dinuclear silver(I) nitrene transfer catalyst with commonly used hypervalent iodine oxidants (PhINSO2Ar), including the first examples of structurally characterized oxidation products obtained under catalytically relevant conditions. Second, we will discuss our efforts towards developing better ligand design principles for dimeric silver(I) complexes, in order to understand how modulating silver–silver interactions affects electronic structure and reactivity. Our results highlight both the promise and the challenges of developing new chemistry from this underappreciated metal.