Anionic N-heterocyclic carbenes featuring weakly coordinating perfluoroalkylphosphorane moieties

Zapf, Ludwig; Radius, Udo; Finze, Maik

doi:10.1039/d3dt01249b

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“…Perfluoroalkyl(fluoro)phosphoranes (C n F 2 n +1 ) m PF 5– m are applied as precursors for conducting salts, ionic liquids, and Brønsted and Lewis acid catalysts and thus cover a wide spectrum of fundamental and applied chemical research . Due to its beneficial properties compared to gaseous PF 5 or toxic and highly corrosive SbF 5 , the liquid Lewis acid tris(pentafluoroethyl)difluorophosphorane (C 2 F 5 ) 3 PF 2 with a boiling point of 91–92 °C has proven to be very useful in laboratory research and applied science. This phosphorane is a stronger Lewis acid with a fluoride ion affinity (FIA) of 405.4 kJ/mol than PF 5 (FIA = 394 kJ/mol) but a weaker Lewis acid than the strong oxidizer AsF 5 (FIA = 426 kJ/mol) .…”

Section: Introductionmentioning

confidence: 99%

Fluoride Abstraction Induced by Tris(pentafluoroethyl)difluorophosphorane: A Convenient Way to Synthesize Cationic N-Heterocyclic Carbene- and Cyclic (Alkyl)(amino)carbene-Ligated Copper Alkyne and Arene Complexes

Riethmann,

Föhrenbacher,

Keiling

et al. 2024

Inorg. Chem.

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We herein report the convenient synthesis of different N-heterocyclic carbene (NHC)-and cyclic (alkyl)(amino)carbene (cAAC)-ligated copper cations using the weakly coordinating tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C 2 F 5 ) 3 PF 3 ] − ). The reaction of the fluorido complexes [(carbene)CuF] (carbene = NHC, cAAC Me ) 2a−2f and the tris(pentafluoroethyl)difluorophosphorane (C 2 F 5 ) 3 PF 2 in the presence of alkynes or arenes led to fluoride transfer from Cu to the phosphorane with formation of the cationic transition metal complexes [(carbene)Cu(L)] + and the weakly coordinating counteranion [(C 2 F 5 ) 3 PF 3 ] − (FAP). Using this method, the complexes [(IDipp)Cu(L)] + FAP − (IDipp = 1,3-bis(2,6-di-isopropylphenyl)-imidazolin-2-ylidene; L = PhC�CPh, 4d; PhC�CMe, 5d), [(cAAC Me )Cu(L)] + FAP − (cAAC Me = 1-(2,6-di-isopropylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene; L = PhC�CPh, 4f; PhC�CMe, 5f), [(SIDipp)Cu(C 6 Me 6 )] + FAP − (6e), (SIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidine-2-ylidene), and [(cAAC Me )Cu(C 6 Me 6 )] + FAP − (6f) have been synthesized and characterized. The complexes [(IDipp)Cu(C 6 Me 6 )] + FAP − (6d) and [(cAAC Me )Cu(C 6 Me 6 )] + FAP − (6f) have been used as catalysts for the copper(I)-catalyzed cycloaddition of benzyl azide to terminal alkynes.

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