The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4]2− (M=Mo, W)1. Issue 33 (15th July 2015)

• Record Type: Journal Article
• Authors: Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A.; Christe, Karl O.
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 33(2015)
• Page Start: 9581
• Page End: 9585
• Publication Date: 2015-07-15
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201504629
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Molybdenum(VI) and tungsten(VI) dioxodiazide, MO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub> (M=Mo, W), were prepared through fluoride–azide exchange reactions between MO<sub>2</sub>F<sub>2</sub> and Me<sub>3</sub>SiN<sub>3</sub> in SO<sub>2</sub> solution. In acetonitrile solution, the fluoride–azide exchange resulted in the isolation of the adducts MO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>⋅2 CH<sub>3</sub>CN. The subsequent reaction of MO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub> with 2, 2′‐bipyridine (bipy) gave the bipyridine adducts (bipy)MO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>. The hydrolysis of (bipy)MoO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub> resulted in the formation and isolation of [(bipy)MoO<sub>2</sub>N<sub>3</sub>]<sub>2</sub>O. The tetraazido anions [MO<sub>2</sub>(N<sub>3</sub>)<sub>4</sub>]<sup>2−</sup> were obtained by the reaction of MO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub> with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>, (bipy)WO<sub>2</sub>(N<sub>3</sub>)<sub>2</sub>, [PPh<sub>4</sub>]<sub>2</sub>[MoO<sub>2</sub>(N<sub>3</sub>)<sub>4</sub>], [PPh<sub>4</sub>]<sub>2</sub>[WO<sub>2</sub>(N<sub>3</sub>)<sub>4</sub>], and [(bipy)MoO<sub>2</sub>N<sub>3</sub>]<sub>2</sub>O by their X‐ray crystal structures.</p> </abstract>