Salts of the Weakly Coordinating Anion [Al(OTeF 5 ) 4 ] – containing Reactive Counterions

Six different salts of the weakly coordinating anion [Al(OTeF 5 ) 4 ] – were synthesized and characterized spectroscopically. The alkali and silver salts M [Al(OTeF 5 ) 4 ] ( M = Ag, Li, Na, K, Rb) were obtained by a protonation reaction involving the Brønsted acid H[Al(OTeF 5 ) 4 ] (solv) . In the case of the lithium and silver salt, crystals of the solvent‐coordinated [Li(thf) 4 ][Al(OTeF 5 ) 4 (thf) 2 ] and [Ag(thf) 6 ][Al(OTeF 5 ) 4 (thf) 2 ] were characterized by low‐temperature X‐ray diffraction, revealing a sixfold coordinated central aluminum atom. By a metathesis reaction, the oxidizing nitrosonium salt [NO][Al(OTeF 5 ) 4 ] was obtained and its reactivity was demonstrated by a reaction with white phosphorus. By low‐temperature NMR spectroscopy the selective formation of [NOP 4 ] + species was confirmed. All of the prepared salts represent useful starting materials for the further introduction of the weakly coordinating anion [Al(OTeF 5 ) 4 ] – into a given system.