The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States

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 r...

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Published inAngewandte Chemie Vol. 126; no. 16; pp. 4202 - 4206
Main Authors Chang, Mu-Chieh, Dann, Thomas, Day, David P., Lutz, Martin, Wildgoose, Gregory G., Otten, Edwin
Format Journal Article
LanguageEnglish
German
Published Weinheim WILEY-VCH Verlag 14.04.2014
WILEY‐VCH Verlag
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Subjects
Accessibility
Backbone
Chemistry
Formazanat
Ligands
Mathematical analysis
N-Liganden
Radicals
Radikalische Liganden
Redoxchemie
Reservoirs
Synthesis
Zinc
Zinc compounds
Zink
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Summary: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. N ist besser als C: In Bis(formazanat)‐Zink‐Komplexen (siehe Bild; Zn gelb, N blau, O rot, Na grün) werden die Formazanat‐Liganden schrittweise und reversibel unter Bildung von Metallaverdazyl‐Radikalen reduziert. Diese Liganden sind den β‐Diketiminaten sehr ähnlich, doch das stickstoffreiche NNCNN‐Rückgrat der Formazanate bietet durch sein Redoxverhalten zusätzliche Perspektiven.
Bibliography:European Research Council - No. ERC-StG-307061 PiHOMER
University of East Anglia
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ArticleID:ANGE201309948
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NWO
G.G.W. and D.P.D. thank the European Research Council for funding (ERC Grant Agreement no..ERC-StG-307061 PiHOMER). G.G.W. thanks the Royal Society for additional support via a University Research Fellowship. T.D. thanks the University of East Anglia for financial support via a Dean's studentship. NWO is gratefully acknowledged for funding (Veni grant to E.O.). We thank Prof. B. de Bruin (University of Amsterdam) for help with VT-EPR experiments and A. Meetsma for useful discussions on the X-ray crystallography.
Royal Society
ERC‐StG‐307061 PiHOMER). G.G.W. thanks the Royal Society for additional support via a University Research Fellowship. T.D. thanks the University of East Anglia for financial support via a Dean’s studentship. NWO is gratefully acknowledged for funding (Veni grant to E.O.). We thank Prof. B. de Bruin (University of Amsterdam) for help with VT‐EPR experiments and A. Meetsma for useful discussions on the X‐ray crystallography.
G.G.W. and D.P.D. thank the European Research Council for funding (ERC Grant Agreement no.
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ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201309948