Following our interest in nitrogen chemistry, we now describe the synthesis, structure, and bonding of labile disilylated diazene, its GaCl3 adduct, and the intriguing trisilylated diazenium ion [(Me3 Si)2 NN-SiMe3 ](+), a dark blue and highly labile (Tdecomp >-30 °C) homoleptic cation of the type [R3 N2 ](+). Although direct silylation of Me3 Si-N=N-SiMe3 failed, the [(Me3 Si)2 N=N-SiMe3](+) ion was generated in a straightforward two-electron oxidation reaction from mercury(II) dihydrazide and Ag[GaCl4]. Moreover, previous structure data of Me3 Si-NN-SiMe3 were revised on the basis of new data.