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Bei der Einelektronenreduktion eines durch eine cyclisches (Alkyl)(amino)carben (CAAC) stabilisierten Arylborylen-Carbonylkomplexes erfolgt die Bildung eines dimeren Borylketyl-Radikalanions, bedingt durch eine intramolekulare Arylmigration zum CO Kohlenstoffatom. Computergestützte Analyse liefert Hinweise auf eine radikalanionische [(CAAC)B(CO)Ar]\(^{.-}\) Zwischenstufe. Weiterführende Reduktion des entstandenen Komplexes liefert ein hoch nukleophiles (Boranyliden)methanolat.
Salts of the tetrakis(pentafluoroethyl)aluminate anion [Al(C\(_{2}\)F\(_{5}\))\(_{2}\)]\(^{-}\) were obtained from AlCl\(_{3}\) and LiC\(_{2}\)F\(_{5}\). They were isolated with different counter‐cations and characterized by NMR and vibrational spectroscopy and mass spectrometry. Degradation of the [Al(C\(_{2}\)F\(_{5}\))\(_{4}\)]\(^{-}\) ion was found to proceed via 1,2‐fluorine shifts and stepwise loss of CF(CF\(_{3}\)) under formation of [(C\(_{2}\)F\(_{5}\))\(_{4-n}\)AlF\(_{n}\)]− (n=1–4) as assessed by NMR spectroscopy and mass spectrometry and supported by results of DFT calculations. In addition, the [(C\(_{2}\)F\(_{5}\))AlF\(_{3}\)]\(^{-}\) ion was structurally characterized.
Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF\(_{3}\))\(_{2}\) group are rare. One reason is that transfer reagents are scarce and metal-based storable reagents are unknown. Herein, a set of Cu\(^{I}\) and Ag\(^{I}\) bis(trifluoromethyl)amido complexes stabilized by N- and P-donor ligands with unprecedented stability are presented. The complexes are stable solids that can even be manipulated in air for a short time. They are bis(trifluoromethyl)amination reagents as shown by nucleophilic substitution and Sandmeyer reactions. In addition to a series of benzylbis(trifluoromethyl)amines, 2-bis(trifluoromethyl)amino acetate was obtained, which, upon hydrolysis, gives the fluorinated amino acid N,N-bis(trifluoromethyl)glycine.
Im Rahmen der vorliegenden Arbeit wurden vier Verbindungsklassen – Borylene, Borole, 9-Borafluorene und 9-Aluminafluorene – untersucht und neue Vertreter dieser Klassen, substituiert mit einem ortho-Dicarba-closo-dodecaboran, dargestellt und auf ihre Reaktivität hin untersucht. Dabei sollte mit den speziellen chemischen Eigenschaften des Carboranylsubstituenten, wie dem elektronenziehenden und gleichzeitig σ-aromatischen Charakter, eine erhöhte Reaktivität der Zielverbindung erreicht werden.