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The Binary Group 4 Azides [PPh 4 ] 2 [Zr(N 3 ) 6 ] and [PPh 4 ] 2 [Hf(N 3 ) 6 ]
Author(s) -
Deokar Piyush,
Vasiliu Monica,
Dixon David A.,
Christe Karl O.,
Haiges Ralf
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201609195
Subject(s) - zirconium , chemistry , azide , crystal structure , hafnium , density functional theory , metal , fluoride , crystallography , group (periodic table) , inorganic chemistry , computational chemistry , organic chemistry
The binary zirconium and hafnium polyazides [PPh 4 ] 2 [M(N 3 ) 6 ] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF 4 by fluoride–azide exchange reactions with Me 3 SiN 3 in the presence of two equivalents of [PPh 4 ][N 3 ]. 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(N 3 ) 4 ], [M(N 3 ) 5 ] − and [M(N 3 ) 6 ] 2− (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.