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

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