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We report on an unexpected reaction between ammonia and potassium ozonide dissolved in liq. NH3 resulting in the formation of peroxynitrite, [ONOO]−, which exclusively happens in the presence of a specific partially fluorinated aniline‐based ammonium cation. High‐resolution structural data of the peroxynitrite anion in cis‐conformation have been obtained. We further studied this molecule anion by single crystal Raman spectroscopy. The cis and trans isomers of peroxynitrite were analysed computationally with respect to their relative energies, the cis‐trans transition barrier and their decomposition pathways to the nitrate anion. By experimentally examining cations decorated with fluorine ligands to different degrees, we demonstrate that fluorine specific interactions play a crucial role in the unexpected formation of peroxynitrite and as a conspicuously structure directing factor for the underlying crystalline solid phases, exhibiting distinct micro‐separations of fluorine and hydrogen enriched regions. [ABSTRACT FROM AUTHOR]

The compounds [Me3N(C6H3(CF3)2)][BF4] and [Me3N(C6H3(CH3)2)][BF4] were synthesized from commercially available starting materials and fully characterized by single-crystal X-ray diffraction, NMR, IR and Raman spectroscopy, as well as mass spectrometry. Both ammonium cations show potential for applications in crystal engineering due to their structure directing properties in the solid state. [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]

The synthesis of [NMe4][AuF4] and [NEt4][AuF4], as well as an improved one-pot synthesis of Cs[AuF4], is reported. The new [AuF4]− salts were structurally characterized by single crystal X-ray diffraction, NMR spectroscopy, vibrational spectroscopy, and mass spectrometry. These salts are the first gold(III) fluoride salts that can be isolated in pure form and are convenient to be used in usual organic solvents for subsequent synthesis. The formation of molecular AuF3 complexes in solution is further reported, characterized as [F3Au(NCCH3)] at low temperature, as [F3Au(py)] and a binuclear derivative which are stable at room temperature. The stability of these species in common organic solvents was investigated and they showed a satisfying stability. [ABSTRACT FROM AUTHOR]