The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States1. Issue 16 (24th February 2014)

• Record Type: Journal Article
• Authors: Chang, Mu‐Chieh; Dann, Thomas; Day, David P.; Lutz, Martin; Wildgoose, Gregory G.; Otten, Edwin
• Is Part Of: Angewandte Chemie international edition. Volume 53:Issue 16(2014)
• Page Start: 4118
• Page End: 4122
• Publication Date: 2014-02-24
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201309948
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The synthesis of bis(formazanate) zinc complexes is described. These complexes have well‐behaved redox‐chemistry, with the ligands functioning as a reversible electron reservoir. This allows the synthesis of bis(formazanate) zinc compounds in three redox states in which the formazanate ligands are reduced to "metallaverdazyl" radicals. The stability of these ligand‐based radicals is a result of the delocalization of the unpaired electron over four nitrogen atoms in the ligand backbone. The neutral, anionic, and dianionic compounds (L₂Zn^0/−1/−2) were fully characterized by single‐crystal X‐ray crystallography, spectroscopic methods, and DFT calculations. In these complexes, the structural features of the formazanate ligands are very similar to well‐known β‐diketiminates, but the nitrogen‐rich (NNCNN) backbone of formazanates opens the door to redox‐chemistry that is otherwise not easily accessible.</p> </abstract>