TY - JOUR A1 - Bischoff, Lisa A. A1 - Riefer, Jarno A1 - Wirthensohn, Raphael A1 - Bischof, Tobias A1 - Bertermann, Rüdiger A1 - Ignat'ev, Nikolai V. A1 - Finze, Maik T1 - Pentafluoroethylaluminates: A Combined Synthetic, Spectroscopic, and Structural Study JF - Chemistry – A European Journal N2 - 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. KW - aluminum KW - fluorine KW - perfluoroalkyl KW - weakly coordinating anions Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-214666 VL - 26 IS - 60 SP - 13615 EP - 13620 ER - TY - JOUR A1 - Drisch, Michael A1 - Bischoff, Lisa A. A1 - Sprenger, Jan A. P. A1 - Hennig, Philipp T. A1 - Wirthensohn, Raphael A1 - Landmann, Johannes A1 - Konieczka, Szymon Z. A1 - Hailmann, Michael A1 - Ignat'ev, Nikolai V. A1 - Finze, Maik T1 - Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination JF - Chemistry – A European Journal N2 - Different types of high‐yield, easily scalable syntheses for cyano(fluoro)borates Kt[BF\(_{n}\)(CN)\(_{4-n}\)] (n=0–2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal‐free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)\(_{2}\){OC(O)Et}]\(^{-}\) to result in [BF(CN)\(_{2}\){OC(O)Et}]\(^{-}\) is described. KW - cyanoborates KW - electrochemical fluorination KW - fluorination KW - fluoroborates KW - ionic liquids Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-216027 VL - 26 IS - 50 SP - 11625 EP - 11633 ER -