Halogenation of Diorganotelluride [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 ]Te n Bu: Synthesis, Molecular and Electronic Structural Investigation of Monoorgano Dihalotelluronium(IV) Cation

A simple methodology for the synthesis of heteroleptic diorganotelluride [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 ]Te n Bu ( 1 ) and homoleptic diorganotelluride [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 ] 2 Te ( 2 ) is reported. The halogenation reactions of diorganotelluride 1 are studied. In particular, the reaction of 1 with Br 2 resulted in the isolation of a monoorgano dibromotelluronium(IV) cation, namely [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 TeBr 2 ] · Br 3 ( [3]·Br 3 ). The reaction of [3]·Br 3 with K 2 PdCl 4 afforded a monoorgano mixed dihalotelluronium(IV) cation, [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 TeClBr] · PdBr 4 ( [4]·PdBr 4 ). When diorganotelluride 1 was treated with I 2 , the reaction afforded the tellurenium(II) cation, [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 Te] · I 2 · I 3 ( [5]·I 2 ·I 3 ). The reaction of 1 with HgCl 2 resulted in the isolation of dimeric diorganoditelluroxonium(IV) cation, [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 Te(µ‐O)] 2 · Hg 2 Cl 6 ( [6]·Hg 2 Cl 6 ). A similar diorganoditelluroxonium(IV) cation, namely [2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 Te(µ‐O)] 2 · 2Br ( [6]·2Br ) was also obtained by the reaction of 1 with Br 2 and NaOH. The crystallographic studies suggest that for each compound, both the N atoms from the pendant arms make strong Intramolecular Chalcogen Bonding (IChB) interactions with the Te center(s). The presence of a strong N→Te IChB interaction in the synthesized compounds was further validated by DFT calculations.