The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States |
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| Authors: | Mu‐Chieh Chang Thomas Dann Dr David P Day Dr Martin Lutz Dr Gregory G Wildgoose Dr Edwin Otten |
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| Institution: | 1. Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands);2. Energy & Materials Laboratory, School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ (UK);3. Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht (The Netherlands) |
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| Abstract: | 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 (L2Zn0/?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. |
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| Keywords: | formazanate N ligands radical ligands redox chemistry zinc |
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