title: The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6].
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 MF4by fluoride-azide exchange reactions with Me3SiN3in 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.
authors.affiliation: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA, 90089, USA.
authors.forename: Piyush
authors.initials: P
authors.lastname: Deokar
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, AL, 35487, USA.
authors.forename: Monica
authors.initials: M
authors.lastname: Vasiliu
authors.affiliation: Department of Chemistry, The University of Alabama, Tuscaloosa, AL, 35487, USA.
authors.forename: David A
authors.initials: DA
authors.lastname: Dixon
authors.affiliation: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA, 90089, USA.
authors.forename: Karl O
authors.initials: KO
authors.lastname: Christe
authors.affiliation: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA, 90089, USA. haiges@usc.edu.
authors.forename: Ralf
authors.identifier: 0000-0003-4151-3593
authors.initials: R
authors.lastname: Haiges
keywords: azides; computational chemistry; hafnium; structure elucidation; zirconium