Binary Bismuth(III) Azides: Bi(N 3 ) 3 , [Bi(N 3 ) 4 ] − , and [Bi(N 3 ) 6 ] 3−

Nitrogen finally meets bismuth: The synthesis of binary bismuth(III) azides BiIII(N3)3, [BiIII(N3)4]−, and [BiIII(N3)6]3− along with their characterization is presented for the first time and closes a chapter in main group chemistry. Bi(N3)3⋅THF qualifies as a good precursor for the generation of binary BiN owing to its low shock and heat sensitivity, in contrast to pure, highly sensitive Bi(N3)3.