Organotellurium(VI) Azides and Halides<sup>†</sup>

The reaction of azide with organotellurium(VI) halides Ph<sub>5</sub>TeBr and <i>cis</i>-(biphen)<sub>2</sub>TeF<sub>2</sub> (biphen = 2,2‘-biphenyldiyl) resulted in the formation and isolation of Ph<sub>5</sub>TeN<sub>3</sub> (<b>1</b>) and <i>cis</i>-(biphen)<sub>2</sub>Te(N<sub>3</sub>)<sub>2</sub> (<b>2</b>), 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<i><sub>x</sub></i>Te(N<sub>3</sub>)<sub>6</sub><sub>-</sub><i><sub>x</sub></i> and Me<i><sub>x</sub></i>Te(N<sub>3</sub>)<sub>6</sub><sub>-</sub><i><sub>x</sub></i> as well as the syntheses and properties of their Ph/Me<i><sub>x</sub></i>TeF<i><sub>y</sub></i> precursors was investigated, including the crystal structure determination of <i>trans</i>-Ph<sub>2</sub>TeF<sub>4</sub> (<b>3</b>). Ab initio and density functional studies of all molecules regarding the structures and electronic populations were performed.