Preparation of the First Manganese(III) and Manganese(IV) Azides

Abstract

Fluoride-azide exchange reactions of Me3SiN3 with MnF2 and MnF3 in acetonitrile resulted in the isolation of Mn(N3)2 and Mn(N3)3 ⋅CH3CN, respectively. While Mn(N3)2 forms [PPh4]2[Mn(N3)4] and (bipy)2Mn(N3)2 upon reaction with PPh4N3 and 2,2'-bipyridine (bipy), respectively, the manganese(III) azide undergoes disproportionation and forms mixtures of [PPh4]2[Mn(N3)4] and [PPh4]2[Mn(N3)6], as well as (bipy)2Mn(N3)2 and (bipy)Mn(N3)4. Neat and highly sensitive Cs2[Mn(N3)6] was obtained through the reaction of Cs2MnF6 with Me3SiN3 in CH3CN.

Homoleptic Poly(nitrato) Complexes of Group 14 Stable at Ambient Conditions

“…This method is akin to the synthesis of the related hexaazido complexes. [32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] The indirect approach (ii) involves the in situ formation of tetranitrates, which are then "trapped" by Lewis acid-base reactions with nitrate anions.…”

The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3)3], [MoO(N3)3⋅2 CH3CN], [(bipy)MoO(N3)3], [MoO(N3)5]2−, [WO(N3)4], and [WO(N3)4⋅CH3CN]

“…[1] Because of their highly endothermic nature,p olyazido compounds are usually explosive and very shock sensitive,rendering the synthesis of molecules with al arge number of azido groups difficult. [1] Because of their highly endothermic nature,p olyazido compounds are usually explosive and very shock sensitive,rendering the synthesis of molecules with al arge number of azido groups difficult.…”

The Vanadium(V) Oxoazides [VO(N3)3], [(bipy)VO(N3)3], and [VO(N3)5]2−

“…[1] Polyazido compounds are highly energetic compounds because of the endothermic nature of the N 3 group. [1] Polyazido compounds are highly energetic compounds because of the endothermic nature of the N 3 group.…”