Redox non-innocence and formation of nitrogen-nitrogen bonds in organometallic reactions

Abstract

The utilization of redox non-innocent ligands and substrates can grant access to new modes of reactivity in organometallic chemistry, allowing for the development of new sustainable methods with earth-abundant catalysts. Through the use of valence tautomerism in nitrogenous ligands and substrates (azides, azobenzene, isodiazenes, etc.), new organometallic reactions have been developed—the atom economical synthesis of important organic molecules such as pyrroles, pyrazoles and imines through titanium redox catalysis and an exploration of the valence tautomerism of an iridium(III)-hydrazido(2-) capable of oxidative addition.