US EPA

3729709 

Journal Article 

The Uranium(VI) Oxoazides [UO2 (N3 )2 ⋅CH3 CN], [(bipy)2 (UO2 )2 (N3 )4 ], [(bipy)UO2 (N3 )3 ](-) , [UO2 (N3 )4 ](2-) , and [(UO2 )2 (N3 )8 ](4) 

Haiges, R; Vasiliu, M; Dixon, DA; Christe, KO 

2017 

Yes 

Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765 

23 

3 

652-664 

English 

27862453 

10.1002/chem.201604154 

WOS:000393625600024 

The reaction between [UO2 F2 ] and an excess of Me3 SiN3 in acetonitrile solution results in fluoride-azide exchange and the uranium(VI) dioxodiazide adduct [UO2 (N3 )2 ⋅CH3 CN] was isolated in quantitative yield. The subsequent reaction of [UO2 (N3 )2 ⋅CH3 CN] with 2,2'-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy)2 (UO2 )2 (N3 )4 ]. The triazido anion [(bipy)UO2 (N3 )3 ](-) was obtained by the reaction of [UO2 (N3 )2 ⋅CH3 CN] with stoichiometric amounts of bipy and the ionic azide [PPh4 ][N3 ]. The reaction of [UO2 (N3 )2 ] with two equivalents of the [PPh4 ][N3 ] resulted in the formation of the mononuclear tetraazido anion [UO2 (N3 )4 ](2-) as well as the azido-bridged binuclear anion [(UO2 )2 (N3 )8 ](4-) . The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy)2 (UO2 )2 (N3 )4 ]⋅CH3 CN, [PPh4 ][(bipy)UO2 (N3 )3 ], [PPh4 ]2 [UO2 (N3 )4 ], [PPh4 ]2 [UO2 (N3 )4 ]⋅2CH3 CN, and [PPh4 ]4 [(UO2 )2 (N3 )8 ]⋅4CH3 CN by their X-ray crystal structures.