Cyclopentadienyl metal teflate (OTeF5) complexes

et al. 2017

Angewandte Chemie

Die neue Lewis‐Säure Al(OTeF5)3 und sein Acetonitril‐Addukt wurden mit Hilfe einer einfachen Syntheseroute in Mengen bis zu 15 g hergestellt und charakterisiert (IR‐, Raman‐Spektroskopie, DFT‐Rechnungen). Ausgehend von der Brønsted‐Säure H[Al(OTeF5)4] wurden mittels Protonierung fünf verschiedene Salze des schwach koordinierenden Anions [Al(OTeF5)4]− in einer zweistufigen Synthese synthetisiert. [Ph4P][Al(OTeF5)4], Cs[Al(OTeF5)4], [Ph3C][Al(OTeF5)4] sowie die protonierten Benzolderivate [C9H13][Al(OTeF5)4] und [C6H7][Al(OTeF5)4] wurden mittels Einkristallröntgenstrukturanalyse und ihrer NMR‐Spektren charakterisiert. Festkörperstrukturen solcher Areniumionen sind selten und wurden in dieser Arbeit auf einem einfachen Weg hergestellt.

Supersäuren basierend auf Pentafluoroorthotelluraten des Aluminiums

Wiesner¹,

Gries²,

et al. 2017

Angewandte Chemie

Superacids Based on Pentafluoroorthotellurate Derivatives of Aluminum

Wiesner¹,

Gries²,

et al. 2017

Angew Chem Int Ed

100

The new Lewis acid Al(OTeF ) and its acetonitrile adduct CH CN→Al(OTeF ) were obtained by a simple one-step synthesis in batches of up to 15 g. Al(OTeF ) and the adduct were characterized by vibrational spectroscopy (IR, Raman) and quantum-chemical calculations. Furthermore, five different salts of the new weakly coordinating anion [Al(OTeF ) ] were prepared in a two-step procedure. [Ph P][Al(OTeF ) ], Cs[Al(OTeF ) ], [Ph C][Al(OTeF ) ], as well as the protonated benzene derivatives [C H ][Al(OTeF ) ] and [C H ][Al(OTeF ) ] were characterized by low-temperature single-crystal X-ray diffraction and NMR spectroscopy. Arenium salts have rarely been characterized in the solid state and were synthesized in this work in a simplified fashion.

Further Development of Weakly Coordinating Cations: Fluorinated Bis(triarylphosphoranylidene)iminium Salts

Mann¹,

Hornberger²,

et al. 2018

Chemistry A European J

So far unknown bis(triarylphosphoranylidene)iminium cations [PPN] with one fluorine atom in para ([PPN-1 ] ), two in meta ([PPN-2 ] ), or three in para and meta positions of the phenyl rings ([PPN-3 ] ) were obtained by a newly developed one-pot reaction. These halogenated [PPN] cations were characterized by IR and Raman spectroscopy in comparison with quantum-chemical calculations, ESI mass spectrometry, NMR spectroscopy, and single-crystal X-ray diffraction. To assess their quality as weakly coordinating cations and the associated ability to stabilize labile anions, the electrostatic potential and fluoride-ion affinity were calculated and compared with those of the unsubstituted and so far unknown perfluorinated [PPN-5 ] cations.