Hidden ligand noninnocence: A combined spectroscopic and computational perspective

Ligand noninnocence has been well-established for transition metal complexes containing diatomics such as NO and O-2, and bidentate chelates like quinones/semiquinones/catecholates, alpha-diimines, and alpha-dithiolenes and also tetrapyrrole macrocycles. The scope of noninnocent ligands is being expanded rapidly for their unique redox properties and catalytic applications. The present contribution attempts to reveal hidden noninnocence of molecules that are often believed to be innocent, which includes 1,3-butadiene dianion, carbodicarbene and peroxo ligand, as well as reductive noninnocence of porphyrins and corroles. (C) 2019 Elsevier B.V. All rights reserved.