Redox-active ligands for chemical, electrochemical, and photochemical molecular conversions

A central issue in the design of reactions and catalysts based on metal complexes is the hybridization of functional ligands with metal atoms. Recent studies have demonstrated that redox-active/non-innocent ligands can potentially act as spectators, moderators, electron/H+/0/- supplier/poolers, cooperators, or actors, depending on their role(s) in the reaction. In this review, we will highlight selected stoichiometric or catalytic reactions driven by substituted ethylenes and dithiolenes, as well as six-membered ligands, such as catecholato, benezendithiolato, aminophenolato, and o-phenelyenediamine derivatives. Chemically, electrochemically, and photochemically induced lability of these ligands can be expected to provide an enriched recipe for a platform toward useful bond-activation and bond-formation processes.(c) 2022 Elsevier B.V. All rights reserved.

Automated summary

The hybridization of functional ligands with metal atoms is a central issue in the design of reactions and catalysts based on metal complexes. Recent studies have shown that redox-active/non-innocent ligands can play various roles, such as spectators, moderators, electron/H+/0/- suppliers/poolers, cooperators, or actors, in reactions. This review highlights stoichiometric or catalytic reactions driven by substituted ethylenes and dithiolenes, as well as six-membered ligands like catecholato, benezendithiolato, aminophenolato, and o-phenelyenediamine derivatives. The chemically, electrochemically, and photochemically induced lability of these ligands is expected to provide a rich platform for useful bond-activation and bond-formation processes.