JACS Au 2021 Aug 6;1(8):1101-1115. Epub 2021 Jul 6.
Homogeneous, Supramolecular and Bio-Inspired Catalysis Group, van 't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
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 () tools to characterize redox-active ligands; () novel synthetic applications of catalytic reactions that make use of redox-active carbene and nitrene substrates at open-shell cobalt-porphyrins; () 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 () utilization of redox-active ligands to influence the spin state of the metal. Read More