The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

被引：7

作者：

Deokar, Piyush ^{[1
,2
]}

Vasiliu, Monica ^{[3
]}

Dixon, David A. ^{[3
]}

Christe, Karl O. ^{[1
,2
]}

Haiges, Ralf ^{[1
,2
]}

机构：

[1] Univ Southern Calif, Loker Hydrocarbon Res Inst, Los Angeles, CA 90089 USA

[2] Univ Southern Calif, Dept Chem, Los Angeles, CA 90089 USA

[3] Univ Alabama, Dept Chem, Box 870336, Tuscaloosa, AL 35487 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 46期

关键词：

azides; computational chemistry; hafnium; structure elucidation; zirconium; POLYAZIDE CHEMISTRY; COORDINATION; COMPLEXES; REACTIVITY; ZIRCONIUM; TITANIUM; ADDUCTS; LIGANDS; SB;

D O I：

10.1002/anie.201609195

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The binary zirconium and hafnium polyazides [PPh4](2)[M(N-3)(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][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.

引用

页码：14348 / 14352

页数：5

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