Taming Electron Transfers: From Breaking Bonds to Creating Molecules

The electron is the ultimate redox reagent to build and reshape molecular structures. Understanding and controlling the parameters underlying dissociative electron transfer (DET) reactivity and its coupling with proton transfer is crucial for combining selectivity, kinetics and energy efficiency in molecular chemistry. Reactivity understanding and mechanistic elements in DET processes are traced back and key examples of current research efforts are presented, demonstrating a large variety of applications. The involvement of DET pathways indeed encompasses a broad range of processes such as photoredox catalysis, CO 2 reduction and alcohol oxidation. Interplay between these experimental examples and fundamental mechanistic study provides a powerful path to the understanding of driving force‐rate relationships, which is crucial for the development of future generations of energy efficient catalytic schemes in redox organic chemistry.