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Herein we report on the formation of the adduct salts [Xe(OTeF5)(pyF)][Al(OTeF5)4] (pyF = C5F5N, C5H3F2N) by abstraction of an –OTeF5 group from Xe(OTeF5)2 with the Lewis superacid Al(OTeF5)3 and subsequent adduct formation of the generated [XeOTeF5]+ cation with fluorinated pyridines. These salts represent the first xenonium cations with the weakly coordinating [Al(OTeF5)4]− anion. The strong oxidizing property of these compounds is further assessed. [ABSTRACT FROM AUTHOR]

The weakly coordinating properties of the [Al(OTeF5)4]– anion were studied by the synthesis and characterization of its tetraalkylammonium salts [NAlk4][Al(OTeF5)4] [Alk4 = –(CH3)4, –(C2H5)4, –(C2H5)3CH3, –(C3H7)4, –(C4H9)4]. The one‐pot synthesis includes formation of the Brønsted acid in 1,2–difluorobenzene, H[Al(OTeF5)4](solv.), and its reaction with [NAlk4]Cl [Alk4 = –(CH3)4, –(C2H5)4, –(C2H5)3CH3, –(C3H7)4, –(C4H9)4] to the corresponding salts. Single crystals were obtained for [N(C4H9)4][Al(OTeF5)4] and characterized by X‐ray diffraction analysis. [ABSTRACT FROM AUTHOR]

The weakly coordinating properties of the [Al(OTeF5)4]– anion were studied by the synthesis and characterization of its tetraalkylammonium salts [NAlk4][Al(OTeF5)4] [Alk4 = –(CH3)4, –(C2H5)4, –(C2H5)3CH3, –(C3H7)4, –(C4H9)4]. The one‐pot synthesis includes formation of the Brønsted acid in 1,2–difluorobenzene, H[Al(OTeF5)4](solv.), and its reaction with [NAlk4]Cl [Alk4 = –(CH3)4, –(C2H5)4, –(C2H5)3CH3, –(C3H7)4, –(C4H9)4] to the corresponding salts. Single crystals were obtained for [N(C4H9)4][Al(OTeF5)4] and characterized by X‐ray diffraction analysis. [ABSTRACT FROM AUTHOR]

Salts of the weakly coordinating anions [Ga(OTeF5)4]− as well as [Ga(Et)(OTeF5)3]− and the neutral Ga2(Et)3(OTeF5)3 were synthesized and characterized by spectroscopic methods and single‐crystal X‐ray diffraction. Ga2(Et)3(OTeF5)3 was formed by treating GaEt3 with pentafluoroorthotelluric acid (HOTeF5) and reacted with PPh4Cl and CPh3Cl to [PPh4][Ga(Et)(OTeF5)3] and [CPh3][Ga(Et)(OTeF5)3]. In contrast, Ag[Ga(OTeF5)4] was prepared from AgOTeF5 and GaCl3 and was used as a versatile starting material for further reactions. Starting with Ag[Ga(OTeF5)4] the substrates [PPh4][Ga(OTeF5)4] and [CPh3][Ga(OTeF5)4] were formed from PPh4Cl and CPh3Cl. [ABSTRACT FROM AUTHOR]

Salts of the weakly coordinating anions [Ga(OTeF5)4]− as well as [Ga(Et)(OTeF5)3]− and the neutral Ga2(Et)3(OTeF5)3 were synthesized and characterized by spectroscopic methods and single‐crystal X‐ray diffraction. Ga2(Et)3(OTeF5)3 was formed by treating GaEt3 with pentafluoroorthotelluric acid (HOTeF5) and reacted with PPh4Cl and CPh3Cl to [PPh4][Ga(Et)(OTeF5)3] and [CPh3][Ga(Et)(OTeF5)3]. In contrast, Ag[Ga(OTeF5)4] was prepared from AgOTeF5 and GaCl3 and was used as a versatile starting material for further reactions. Starting with Ag[Ga(OTeF5)4] the substrates [PPh4][Ga(OTeF5)4] and [CPh3][Ga(OTeF5)4] were formed from PPh4Cl and CPh3Cl. [ABSTRACT FROM AUTHOR]

Six different salts of the weakly coordinating anion [Al(OTeF5)4]– were synthesized and characterized spectroscopically. The alkali and silver salts M[Al(OTeF5)4] (M = Ag, Li, Na, K, Rb) were obtained by a protonation reaction involving the Brønsted acid H[Al(OTeF5)4](solv). In the case of the lithium and silver salt, crystals of the solvent‐coordinated [Li(thf)4][Al(OTeF5)4(thf)2] and [Ag(thf)6][Al(OTeF5)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(OTeF5)4] was obtained and its reactivity was demonstrated by a reaction with white phosphorus. By low‐temperature NMR spectroscopy the selective formation of [NOP4]+ species was confirmed. All of the prepared salts represent useful starting materials for the further introduction of the weakly coordinating anion [Al(OTeF5)4]– into a given system. [ABSTRACT FROM AUTHOR]