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

Fluoride‐azide exchange reactions of Me 3 SiN 3 with MnF 2 and MnF 3 in acetonitrile resulted in the isolation of Mn(N 3 ) 2 and Mn(N 3 ) 3 ⋅CH 3 CN, respectively. While Mn(N 3 ) 2 forms [PPh 4 ] 2 [Mn(N 3 ) 4 ] and (bipy) 2 Mn(N 3 ) 2 upon reaction with PPh 4 N 3 and 2,2′‐bipyridine (bipy), respectively, the manganese(III) azide undergoes disproportionation and forms mixtures of [PPh 4 ] 2 [Mn(N 3 ) 4 ] and [PPh 4 ] 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 Cs 2 MnF 6 with Me 3 SiN 3 in CH 3 CN.