Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play.

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected for many decades by careful selection of metal centers and ligands, giving rise to synthetic methods with unparalleled efficiency and chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful tool to dramatically alter the outcome of catalytic reactions, providing access to innovative pathways with remarkable synthetic potential. In this context, the adoption of photochemical conditions as a mainstream strategy to drive organic reactions has unveiled exciting opportunities to exploit the rich excited-state framework of transition metals for catalytic applications. This Perspective examines advances in the application of transition metal complexes as standalone photocatalysts, exploiting the innate reactivity of their excited states beyond their common use as photoredox catalysts. An account of relevant examples is dissected to provide a discussion on the electronic reorganization, the orbitals involved, and the associated reactivity of different types of excited states. This analysis aims to provide practitioners with fundamental principles and guiding strategies to understand, design, and apply light-activation strategies to homogeneous transition metal catalysis for organic synthesis.