@article{SchneiderTanzerKrauelDeutschetal.2021, author = {Schneider, Leon N. and Tanzer Krauel, Eva-Maria and Deutsch, Carl and Urbahns, Klaus and Bischof, Tobias and Maibom, Kristina A. M. and Landmann, Johannes and Keppner, Fabian and Kerpen, Christoph and Hailmann, Michael and Zapf, Ludwig and Knuplez, Tanja and Bertermann, R{\"u}diger and Ignat'ev, Nikolai V. and Finze, Maik}, title = {Stable and Storable N(CF\(_{3}\))\(_{2}\) Transfer Reagents}, series = {Chemistry—A European Journal}, volume = {27}, journal = {Chemistry—A European Journal}, number = {42}, doi = {10.1002/chem.202101436}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256890}, pages = {10973-10978}, year = {2021}, abstract = {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.}, language = {en} } @article{DrischBischoffSprengeretal.2020, author = {Drisch, Michael and Bischoff, Lisa A. and Sprenger, Jan A. P. and Hennig, Philipp T. and Wirthensohn, Raphael and Landmann, Johannes and Konieczka, Szymon Z. and Hailmann, Michael and Ignat'ev, Nikolai V. and Finze, Maik}, title = {Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination}, series = {Chemistry - A European Journal}, volume = {26}, journal = {Chemistry - A European Journal}, number = {50}, doi = {10.1002/chem.202002324}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-216027}, pages = {11625 -- 11633}, year = {2020}, abstract = {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 Br{\o}nsted 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.}, language = {en} } @article{LandmannHennigIgnat'evetal.2017, author = {Landmann, Johannes and Hennig, Philipp T. and Ignat'ev, Nikolai V. and Finze, Maik}, title = {Borylation of fluorinated arenes using the boron centred nucleophile B(CN)\(_{3}\)\(^{2-}\) - a unique entry to aryltricyanoborates}, series = {Chemical Science}, volume = {8}, journal = {Chemical Science}, number = {9}, doi = {10.1039/c7sc02249b}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-170417}, pages = {5962-5968}, year = {2017}, abstract = {The potassium salt of the boron-centred nucleophile B(CN)\(_{3}\)\(^{2-}\)(1) readily reacts with perfluorinated arenes, such as hexafluorobenzene, decafluorobiphenyl, octafluoronaphthalene and pentafluoropyridine, which results in KF and the K\(^{+}\) salts of the respective borate anions with one {B(CN)\(_{3}\)} unit bonded to the (hetero)arene. An excess of K\(_{2}\)1 leads to the successive reaction of two or, in the case of perfluoropyridine, even three C-F moieties and the formation of di- and trianions, respectively. Moreover, all of the 11 partially fluorinated benzene derivatives, C\(_{6}\)F\(_{6-n}\)H\(_{n}\) (n = 1-5), generally react with K\(_{2}\)1 to give new tricyano(phenyl)borate anions with high chemo- and regioselectivity. A decreasing number of fluorine substituents on benzene results in a decrease in the reaction rate. In the cases of partially fluorinated benzenes, the addition of LiCl is advantageous or even necessary to facilitate the reaction. Also, pentafluorobenzenes R-C\(_{6}\)F\(_{5}\) (R = -CN, -OMe, -Me, or -CF\(_{3}\)) react via C-F/C-B exchange that mostly occurs in the para position and to a lesser extent in the meta or ortho positions. Most of the reactions proceed via an S\(_{N}\)Ar mechanism. The reaction of 1,4-F\(_{2}\)C\(_{6}\)H\(_{4}\) with K\(_{2}\)1 shows that an aryne mechanism has to be considered in some cases as well. In summary, a wealth of new stable tricyano(aryl)borates have been synthesised and fully characterized using multi-NMR spectroscopy and most of them were characterised using single-crystal X-ray diffraction.}, language = {en} }