@article{FoehrenbacherKrahfussZapfetal.2021, author = {F{\"o}hrenbacher, Steffen A. and Krahfuss, Mirjam J. and Zapf, Ludwig and Friedrich, Alexandra and Ignat'ev, Nikolai V. and Finze, Maik and Radius, Udo}, title = {Tris(pentafluoroethyl)difluorophosphorane: a versatile fluoride acceptor for transition metal chemistry}, series = {Chemistry Europe}, volume = {27}, journal = {Chemistry Europe}, number = {10}, doi = {10.1002/chem.202004885}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256665}, pages = {3504-3516}, year = {2021}, abstract = {Fluoride abstraction from different types of transition metal fluoride complexes [L\(_n\)MF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C\(_2\)F\(_5\))\(_3\)PF\(_2\) to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C\(_2\)F\(_5\))\(_3\)PF\(_3\)]\(^-\)) is reported. (C\(_2\)F\(_5\))\(_3\)PF\(_2\) reacted with trans-[Ni(iPr\(_2\)Im)\(_2\)(Ar\(^F\))F] (iPr2Im=1,3-diisopropylimidazolin-2-ylidene; Ar\(^F\)=C\(_6\)F\(_5\), 1 a; 4-CF\(_3\)-C\(_6\)F\(_4\), 1 b; 4-C\(_6\)F\(_5\)-C\(_6\)F\(_4\), 1 c) through fluoride transfer to form the complex salts trans-[Ni(iPr\(_2\)Im)\(_2\)(solv)(Ar\(^F\))]FAP (2 a-c[solv]; solv=Et\(_2\)O, CH\(_2\)Cl\(_2\), THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh\(_3\), solvent coordination was suppressed and the complexes trans-[Ni(iPr\(_2\)Im)\(_2\)(PPh\(_3\))(C\(_6\)F\(_5\))]FAP (trans-2 a[PPh\(_3\)]) and cis-[Ni(iPr\(_2\)Im)\(_2\)(Dipp\(_2\)Im)(C\(_6\)F\(_5\))]FAP (cis-2 a[Dipp\(_2\)Im]) (Dipp\(_2\)Im=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp\(_2\)Im)CuF] (3) in CH\(_2\)Cl\(_2\) or 1,2-difluorobenzene led to the isolation of [{(Dipp\(_2\)Im)Cu}\(_2\)]\(^2\)\(^+\)2 FAP\(^-\) (4). Subsequent reaction of 4 with PPh\(_3\) and different carbenes resulted in the complexes [(Dipp\(_2\)Im)Cu(LB)]FAP (5 a-e, LB=Lewis base). In the presence of C6Me6, fluoride transfer afforded [(Dipp\(_2\)Im)Cu(C\(_6\)Me\(_6\))]FAP (5 f), which serves as a source of [(Dipp\(_2\)Im)Cu)]\(^+\). Fluoride abstraction of [Cp\(_2\)TiF\(_2\)] (7) resulted in the formation of dinuclear [FCp\(_2\)Ti(μ-F)TiCp\(_2\)F]FAP (8) (Cp=η\(^5\)-C\(_5\)H\(_5\)) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.}, language = {en} } @article{BischoffRieferWirthensohnetal.2020, author = {Bischoff, Lisa A. and Riefer, Jarno and Wirthensohn, Raphael and Bischof, Tobias and Bertermann, R{\"u}diger and Ignat'ev, Nikolai V. and Finze, Maik}, title = {Pentafluoroethylaluminates: A Combined Synthetic, Spectroscopic, and Structural Study}, series = {Chemistry - A European Journal}, volume = {26}, journal = {Chemistry - A European Journal}, number = {60}, doi = {10.1002/chem.202000667}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-214666}, pages = {13615 -- 13620}, year = {2020}, abstract = {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.}, language = {en} }