The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]. Issue 46 (13th October 2016)

• Record Type: Journal Article
• Authors: Deokar, Piyush; Vasiliu, Monica; Dixon, David A.; Christe, Karl O.; Haiges, Ralf
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 46(2016)
• Page Start: 14350
• Page End: 14354
• Publication Date: 2016-10-13
• Subjects: azides -- computational chemistry -- hafnium -- structure elucidation -- zirconium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201609195
• Languages: English
• ISSNs: 1433-7851

Abstract

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 Me3 SiN3 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. Abstract : Nothing but N : Binary zirconium and hafnium polyazides [PPh4 ]2 [M(N3 )6 ] (M=Zr, Hf) were prepared from the corresponding metal fluorides MF4 and two equivalents of [PPh4 ][N3 ] by fluoride–azide exchange with Me3 SiN3 . Both novel azido salts were characterized by X‐ray crystal structure analysis, vibrational and NMR spectra, and decomposition temperatures.