Stabilization of 2-Pyridyltellurium(II) Derivatives by Oxidorhenium(V) Complexes

• Published in: Chemistry an international journal 2023-06, Vol.5 (2), p.934-947
• Main Authors: da Silva, Felipe Dornelles, Roca Jungfer, Maximilian, Hagenbach, Adelheid, Lang, Ernesto Schulz, Abram, Ulrich
• Format: Article
• Language: English
• Subjects: Chlorides; Crystals; DFT; Ethanol; Ligands; Oxidation; oxido bridge; Radiation; Rhenium; Solvents; Tellurium; Visualization; Zwitterions
• ISSN: 2624-8549; 2624-8549
• DOI: 10.3390/chemistry5020063

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)p⏠y}+ 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.