Isolation of a Labile Homoleptic Diazenium Cation

Following our interest in nitrogen chemistry, we now describe the synthesis, structure, and bonding of labile disilylated diazene, its GaCl 3 adduct, and the intriguing trisilylated diazenium ion [(Me 3 Si) 2 NN‐SiMe 3 ] + , a dark blue and highly labile ( T decomp >−30 °C) homoleptic cation of the type [R 3 N 2 ] + . Although direct silylation of Me 3 Si‐NN‐SiMe 3 failed, the [(Me 3 Si) 2 NN‐SiMe 3 ] + ion was generated in a straightforward two‐electron oxidation reaction from mercury(II) dihydrazide and Ag[GaCl 4 ]. Moreover, previous structure data of Me 3 Si‐NN‐SiMe 3 were revised on the basis of new data.