Abstract

AbstractA first example of an aryltellurium(II) compound with three different bonding modes to iodine featuring covalent and non‐covalent bonds such as two orthogonal, ambiphilic σ‐hole interactions is introduced: [MesTe(I)(I2)(I3)]−. It is a member of a series of mesityltellurenyl anions, which are formed during reactions of (MesTe)2 with ZnI2, phenanthroline (phen) and iodine. [Zn(phen)3][MesTe(I)2] (1), [Zn(phen)3][{MesTe(I)‐(I)…Te(I)Mes}{MesTeI2}] (2) and [Zn(phen)3][MesTe(I)(I2)(I3)][MesTeI2] (3) are isolated depending on the amount of iodine used. The products contain tellurium atoms bonded to a variety of iodine species (I−, μ2‐I−, I2 and I3−) and are, thus, perfectly suitable to explore the amphiphilic behavior of tellurium(II) and its relevance for the formation of non‐covalent bonds, where tellurium acts as both donor and acceptor simultaneously. The character of chalcogen and halogen bonds are evaluated by the combination of crystallographic data and computational methods.

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