Cooperation between p-Block Elements and Redox-Active Ligands: Stoichiometric and Catalytic Transformations.

Abstract

The relevance acquired by redox-active ligands in modern catalysis stems from their facile delivery and acceptance of electrons, either to the metal they coordinate to, or directly to an incoming substrate that also binds the central metal. Doing that, they generate coordinated radicals and provide access to more than one spin state during the catalytic cycle. As a consequence, the new reaction barriers are reduced when compared to similar processes that are restricted to a single spin surface. The principles that govern this genuine approach to catalyst design are well-established, and their implementation has allowed the development of synthetically useful catalytic transformations; however, the extension of the concept to species in which p-block elements take the role of central atoms remains largely underdeveloped. Through discussion of the key achievements and recent progress, this Concept Article highlights this original approach to designing (organo)catalysts, discloses the progress achieved, and also reveals the many shortcomings that still exist in the field.