Synthesis and structural features of new aryltellurenyl iodides

(TmpTe)2 (tmp = 2,3,5,6-tetramethylphenyl) reacts with I2 to yield the sterically stabilized arenetellurenyl iodide [tmpTeI]2 (1). The reaction of 1 with I2 gives [tmpTe(I)I2] (2), which formally results from the association of the intermediary RTeI with I2 under oxidation to TeIII. Compound 1 reacts also with (PyH)I to give the hypervalent, 3c−4e, T-shaped complex (PyH)[tmpTeI2] (3). The reaction of 3 with I2 gives (PyH)[tmpTeI3(I3)] (4), a rare example of TeIV compound in which a View the MathML sourceI3- chain appears as component of the complex and not as solvate. Complex 3 reacts also with I2 in the presence of water with hydrolysis of the R−Te bond, leading to the structurally rare compounds (PyH)2[TeI4(μ-I)2TeI4] (5), [(tmp)2TeI2] (6) and (PyH)2[TeI6]·I2 (7). The structural features of the products are discussed, as well as the synthetic procedures.