Zwitterionic compounds such as pyridine-containing tellurenyl compounds are interesting building blocks for heterometallic assemblies. They can act as ambiphilic donor/acceptors as is shown by the products of reactions of the zwitterions HpyTeCl2 or HCF3pyTeCl2 with the rhenium(V) complex [ReOCl3(PPh3)2]. The products have a composition of [ReO2Cl(pyTeCl)(PPh3)2] and [ReO2Cl(CF3pyTeCl)(PPh3)2] with central {O=Re=O…Te(Cl)p𝑦}+ units. The Re-O bonds in the products are elongated by approximately 0.1 Å compared with those to the terminal oxido ligands and establish Te…O contacts. Thus, the normally easily assigned concept of oxidation states established at the two metal ions becomes questionable (ReV/TeII vs. ReIII/TeIV). A simple bond length consideration rather leads to a description with the coordination of a mesityltellurenyl(II) chloride unit to an oxido ligand of the Re(V) center, but the oxidation of the tellurium ion and the formation of a tellurinic acid chloride cannot be ruled out completely from an analysis of the solid-state structures. DFT calculations (QTAIM, NBO analysis) give clear support for the formation of a Re(V) dioxide complex donating into an organotellurium(II) chloride and the alternative description can at most be regarded as a less favored resonance structure.
