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- Title
The Binary Group 4 Azides [PPh<sub>4</sub>]<sub>2</sub>[Zr(N<sub>3</sub>)<sub>6</sub>] and [PPh<sub>4</sub>]<sub>2</sub>[Hf(N<sub>3</sub>)<sub>6</sub>].
- Authors
Deokar, Piyush; Christe, Karl O.; Haiges, Ralf; Vasiliu, Monica; Dixon, David A.
- Abstract
The binary zirconium and hafnium polyazides [PPh4]2[M(N3)6] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF4 by fluoride-azide exchange reactions with Me3SiN3 in the presence of two equivalents of [PPh4][N3]. The novel polyazido compounds were characterized by their vibrational spectra and their X-ray crystal structures. Both anion structures provide experimental evidence for near-linear M-N-N coordination of metal azides. The species [M(N3)4], [M(N3)5]− and [M(N3)6]2− (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.
- Subjects
ZIRCONIUM; BINARY metallic systems; AZIDES; FLUORIDES; HAFNIUM compounds
- Publication
Angewandte Chemie International Edition, 2016, Vol 55, Issue 46, p14350
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201609195