@article{FoehrenbacherZehKrahfussetal.2021, author = {F{\"o}hrenbacher, Steffen A. and Zeh, Vivien and Krahfuss, Mirjam J. and Ignat'ev, Nikolai V. and Finze, Maik and Radius, Udo}, title = {Tris(pentafluoroethyl)difluorophosphorane and N-Heterocyclic Carbenes: Adduct Formation and Frustrated Lewis Pair Reactivity}, series = {European Journal of Inorganic Chemistry}, volume = {2021}, journal = {European Journal of Inorganic Chemistry}, number = {20}, doi = {10.1002/ejic.202100183}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257386}, pages = {1941-1960}, year = {2021}, abstract = {The synthesis and characterization of Lewis acid/base adducts between tris(pentafluoroethyl)difluorophosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) and selected N-heterocyclic carbenes (NHCs) R\(_{2}\)Im (1,3-di-organyl-imidazolin-2-ylidene) and phosphines are reported. For NHCs with small alkyl substituents at nitrogen (R=Me, nPr, iPr) the adducts NHC ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) (2 a-h) were isolated. The reaction with the sterically more demanding NHCs Dipp\(_{2}\)Im (1,3-bis-(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene) (1 i) and tBu\(_{2}\)Im (1,3-di-tert-butyl-imidazolin-2-ylidene) (1 j) afforded the aNHC adducts 3 i and 3 j (a denotes "abnormal" NHC coordination via a backbone carbon atom). The use of tBuMeIm (1-tert-butyl-3-methyl-imidazolin-2-ylidene) (1 m) led to partial decomposition of the NHC and formation of the salt [tBuMeIm-H][MeIm ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)] (4 m). The phosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) forms adducts with PMe\(_{3}\) but does not react with PPh\(_{3}\) or PCy\(_{3}\). The mer-cis isomer of literature-known Me\(_{3}\)P ⋅ PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) (5 a) was structurally characterized. Mixtures of the phosphorane PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) and the sterically encumbered NHCs tBu\(_{2}\)Im, Dipp\(_{2}\)Im, and Dipp\(_{2}\)Im\(^{H2}\) (1,3-bis-(2,6-di-iso-propylphenyl)-imidazolidin-2-ylidene) (1 k) showed properties of FLPs (Frustrated Lewis Pairs) as these mixtures were able to open the ring of THF (tetrahydrofuran) to yield NHC-(CH\(_{2}\))\(_{4}\)O-PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\) 6 i-k. Furthermore, the deprotonation of the weak C-H acids CH\(_{3}\)CN, acetone, and ethyl acetate was achieved, which led to the formation of the corresponding imidazolium salts and the phosphates [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(CH\(_{2}\)CN)]\(^{-}\) (7), [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(OC(=CH\(_{2}\))CH\(_{3}\))]\(^{-}\) (8) and [PF\(_{2}\)(C\(_{2}\)F\(_{5}\))\(_{3}\)(CH\(_{2}\)CO\(_{2}\)Et)]\(^{-}\) (9).}, language = {en} } @article{HaeringKerpenRibbecketal.2022, author = {H{\"a}ring, Mathias and Kerpen, Christoph and Ribbeck, Tatjana and Hennig, Philipp T. and Bertermann, R{\"u}diger and Ignat'ev, Nikolai V. and Finze, Maik}, title = {Dismutation of Tricyanoboryllead Compounds: The Homoleptic Tetrakis(tricyanoboryl)plumbate Tetraanion}, series = {Angewandte Chemie}, volume = {61}, journal = {Angewandte Chemie}, number = {24}, doi = {10.1002/anie.202202882}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-318257}, year = {2022}, abstract = {A series of unprecedently air-stable (tricyanoboryl)plumbate anions was obtained by the reaction of the boron-centered nucleophile B(CN)\(_{3}\)\(^{2-}\) with triorganyllead halides. Salts of the anions [R\(_{3}\)PbB(CN)\(_{3}\)]\(^{-}\) (R=Ph, Et) were isolated and found to be stable in air at room temperature. In the case of Me\(_{3}\)PbHal (Hal=Cl, Br), a mixture of the anions [Me\(_{4-n}\)Pb{B(CN)\(_{3}\)}\(_{n}\)]\(^{n-}\) (n=1, 2) was obtained. The [Et\(_{3}\)PbB(CN)\(_{3}\)]- ion undergoes stepwise dismutation in aqueous solution to yield the plumbate anions [Et4\(_{4-n}\)Pb{B(CN)\(_{3}\)}\(_{n}\)]\(^{n-}\) (n=1-4) and PbEt\(_{4}\) as by-product. The reaction rate increases with decreasing pH value of the aqueous solution or by bubbling O\(_{2}\) through the reaction mixture. Adjustment of the conditions allowed the selective formation and isolation of salts of all anions of the series [Et\(_{4-n}\)Pb{B(CN)\(_{3}\)}\(_{n}\)]\(^{n-}\) (n=2-4) including the homoleptic tetraanion [Pb{B(CN)\(_{3}\)}\(_{4}\)]\(^{4-}\).}, language = {en} } @article{ZapfPetersBertermannetal.2022, author = {Zapf, Ludwig and Peters, Sven and Bertermann, R{\"u}diger and Radius, Udo and Finze, Maik}, title = {Tricyanoborane-Functionalized Anionic N-Heterocyclic Carbenes: Adjustment of Charge and Stereo-Electronic Properties}, series = {Chemistry - A European Journal}, volume = {28}, journal = {Chemistry - A European Journal}, number = {39}, doi = {10.1002/chem.202200275}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-287200}, year = {2022}, abstract = {The 1-methyl-3-(tricyanoborane)imidazolin-2-ylidenate anion (2) was obtained in high yield by deprotonation of the B(CN)3-methylimidazole adduct 1. Regarding charge and stereo-electronic properties, anion 2 closes the gap between well-known neutral NHCs and the ditopic dianionic NHC, the 1,3-bis(tricyanoborane)imidazolin-2-ylidenate dianion (IIb). The influence of the number of N-bonded tricyanoborane moieties on the σ-donating and π-accepting properties of NHCs was assessed by quantum chemical calculations and verified by experimental data on 2, IIb, and 1,3-dimethylimidazolin-2-ylidene (IMe, IIa). Therefore NHC 2, which acts as a ditopic ligand via the carbene center and the cyano groups, was reacted with alkyl iodides, selenium, and [Ni(CO)\(_{4}\)] yielding alkylated imidazoles 3 and 4, the anionic selenium adduct 5, and the anionic nickel tricarbonyl complex 8, respectively. The results of this study prove that charge, number of coordination sites, buried volume (\%V\(_{bur}\)) and σ-donor and π-acceptor abilities of NHCs can be effectively fine-tuned via the number of tricyanoborane substituents.}, language = {en} } @article{CataldiRaschigGutmannetal.2023, author = {Cataldi, Eleonora and Raschig, Martina and Gutmann, Marcus and Geppert, Patrick T. and Ruopp, Matthias and Schock, Marvin and Gerwe, Hubert and Bertermann, R{\"u}diger and Meinel, Lorenz and Finze, Maik and Nowak-Kr{\´o}l, Agnieszka and Decker, Michael and L{\"u}hmann, Tessa}, title = {Amber Light Control of Peptide Secondary Structure by a Perfluoroaromatic Azobenzene Photoswitch}, series = {ChemBioChem}, volume = {24}, journal = {ChemBioChem}, number = {5}, doi = {10.1002/cbic.202200570}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-312480}, year = {2023}, abstract = {The incorporation of photoswitches into the molecular structure of peptides and proteins enables their dynamic photocontrol in complex biological systems. Here, a perfluorinated azobenzene derivative triggered by amber light was site-specifically conjugated to cysteines in a helical peptide by perfluoroarylation chemistry. In response to the photoisomerization (trans→cis) of the conjugated azobenzene with amber light, the secondary structure of the peptide was modulated from a disorganized into an amphiphilic helical structure.}, language = {en} }