Photocatalytic Activity of Diverse Organic Radical Anions: Catalyst Discovery Enables Cleavage of Strong C(sp2)–N and C(sp2)–O Bonds

Herein, we leverage electrochemistry to examine the photocatalytic activity of a range of structurally diverse persistent radical anions and find that many are effective electrophotocatalysts. These studies uncover a new electron-primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp2)–N and C(sp2)–O bonds even when reduction potentials hundreds of mV more negative than Li0 are required. We illustrated several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employed electrochemical current measurements to perform a reaction progress kinetic analysis that revealed that the improved activity of this new catalyst was a consequence of an enhanced stability profile.