SILYL-NITROGEN COMPOUNDS,¹ 11: SYNTHESIS AND CHARACTERISATION OF TETRASILAPHOSPHA AND TETRASILA-ARSA TETRAZENES

Abstract

Lithylated bis(trimethylsilyl)hydrazines, Li₂N₂(SiMe₃)₂ and LiH N₂(SiMe₃)₂ react with (Me₃Si)₂NECI₂ (E ˭ P or As) to form hetero atom incorporated tetrazenes, 1,3.4,4-tetrakis(trimethyIsilyl)-2-phospha-I-tetrazene (Me₃Si)₂N‒ N(SiMe₃)‒ P˭NSiMe₃ and 1,1,4,4-tetrakis-(trimethylsilyl)-2-arsa-2-tetrazene (Me₃Si)₂N‒N˭As‒N(SiMe₃)₂. The former thermolyses primarily into trisila-phosphatriazene (Me₃Si)₂N‒P˭NSiMe₃ and tetrasilahydrazine (Me₃Si)₄N₂, whereas, the latter forms tris(trimethylsily1)hydrazine (Me₃Si)₃N₂H. Phosphatetrazene interacts with CH₃OH in an oxida-tive addition reaction to form [tris(trimethylsilyl)-hydrazino]-(trimethylsilylimino)-(methoxy)-phosphorane, (Me₃Si)₂N‒N(SiMe₃)‒PH(OCH,)(˭NSiMe₃), whereas, arsatetrazene undergoes cleavage reaction to yield (Me₃Si)₃N₂H.

Key Words:

• Tetrasila-2-phospha-I-tetrazene
• tetrasila-2-arsa-2-tetrazene
• synthesis
• characterization
• thermolysis
• oxidative addition.