Exploring Indium Teflates: From Neutral In(OTeF ₅ ) ₃ (THF) ₃ to Anionic Complexes [In(OTeF ₅ ) ₄ (THF) ₂ ] – and [In(OTeF ₅ ) ₆ ] ³–

This study explores the synthesis and characterization of novel indium‐based pentafluoroorthotellurate (teflate) derivatives. It introduces a series of indium(III) teflate mono‐ and trianions, including [In(OTeF 5 ) 4 (THF) 2 ] – and [In(OTeF 5 ) 6 ] 3– . The research utilizes low‐temperature single‐crystal X‐ray diffraction, IR, and NMR spectroscopy to provide the first structural insights into these indium(III) teflate anions. The neutral Lewis acid [In(OTeF 5 ) 3 ] is successfully synthesized as its THF adduct [In(OTeF 5 ) 3 (THF) 3 ] via a salt metathesis reaction with InCl 3 and AgOTeF 5. Quantum‐chemical calculations and catalytic tests highlight the pronounced Lewis acidity of the indium center in these compounds.