Organotellurium(VI) Azides and Halides^†

The reaction of azide with organotellurium(VI) halides Ph₅TeBr and cis-(biphen)₂TeF₂ (biphen = 2,2‘-biphenyldiyl) resulted in the formation and isolation of Ph₅TeN₃ (1) and cis-(biphen)₂Te(N₃)₂ (2), which are the first tellurium(VI)-azide species. In addition to spectroscopic data, both crystal structures have been determined. Furthermore, the stability of possible Te(VI) species with higher azide contents Ph_xTe(N₃)_6-x and Me_xTe(N₃)_6-x as well as the syntheses and properties of their Ph/Me_xTeF_y precursors was investigated, including the crystal structure determination of trans-Ph₂TeF₄ (3). Ab initio and density functional studies of all molecules regarding the structures and electronic populations were performed.