Mechanistic Studies of Catalytic Nitrene-Transfer Reactions Involving Redox-Active Ligands and Substrates

This chapter describes catalytic (redox-active) nitrene transfer reactions aided by redox-active ligands. Several case studies are outlined, and spectroscopic techniques and mechanistic studies are discussed. The chapter highlights the various manners wherein the nitrene radical moiety can be formed and transferred to a substrate, i.e. (i) metal-to-substrate single-electron transfer, (ii) ligand-to-substrate single-electron transfer, (iii) spin-changing processes, and (iv) electron transfer coupled to spin-flips. Importantly, the described catalytic systems all rely on the use of a redox-active ligand and/or redox-active nitrene moiety to achieve the observed reactivity in C-N, N-N, and S-N bond formation.