Controlling Radical-Type Single-Electron Elementary Steps in Catalysis with Redox-Active Ligands and Substrates

[Image: see text] Advances in (spectroscopic) characterization of the unusual electronic structures of open-shell cobalt complexes bearing redox-active ligands, combined with detailed mapping of their reactivity, have uncovered several new catalytic radical-type protocols that make efficient use of the synergistic properties of redox-active ligands, redox-active substrates, and the metal to which they coordinate. In this perspective, we discuss the tools available to study, induce, and control catalytic radical-type reactions with redox-active ligands and/or substrates, contemplating recent developments in the field, including some noteworthy tools, methods, and reactions developed in our own group. The main topics covered are (i) tools to characterize redox-active ligands; (ii) novel synthetic applications of catalytic reactions that make use of redox-active carbene and nitrene substrates at open-shell cobalt–porphyrins; (iii) development of catalytic reactions that take advantage of purely ligand- and substrate-based redox processes, coupled to cobalt-centered spin-changing events in a synergistic manner; and (iv) utilization of redox-active ligands to influence the spin state of the metal. Redox-active ligands have emerged as useful tools to generate and control reactive metal-coordinated radicals, which give access to new synthetic methodologies and intricate (electronic) structures, some of which are yet to be exposed.