A Mechanistic Analysis of Metallaphotoredox C-N Coupling: Photocatalysis Initiates and Perpetuates Ni(I)/Ni(III) Coupling Activity.

The combined use of reaction kinetic analysis, ultrafast spectroscopy, and stoichiometric organometallic studies has enabled the elucidation of the mechanistic underpinnings to a photocatalytic C-N cross-coupling reaction. Steady-state and ultrafast spectroscopic techniques were used to track the excited-state evolution of the employed iridium photocatalyst, determine the resting states of both iridium and nickel catalysts, and uncover the photochemical mechanism for reductive activation of the nickel co- catalyst. Stoichiometric organometallic studies along with a comprehensive kinetic study of the reaction, including rate-driving force analysis, unveiled the crucial role of photocatalysis in both initiating and sustaining a Ni(I)/Ni(III) cross-coupling mechanism. The insights gleaned from this study further enabled the discovery of a new photocatalyst providing a >30-fold rate increase.