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7068517 
Journal Article 
Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry 
Radius, U; Föhrenbacher, SA; Krahfuss, MJ; Zapf, L; Friedrich, A; Ignat'ev, NV; Finze, M; , 
2020 
Yes 
Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765 
English 
33241855 
Fluoride abstraction from different types of transition metal fluorido complexes [LnM-F] using the Lewis acid tris-(penta-fluoro-ethyl)-difluoro-phosphorane (C2F5)3PF2 to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counter-ion (FAP anion, [(C2F5)3PF3 ]-) is reported. (C2 F5 )3PF2 reacted with trans-[Ni(iPr2Im)2(F)(ArF )]( i Pr 2 Im=1,3-di(iso -propyl)-imidazolin-2-ylidene; ArF=C6F5 1a ; 4-CF3-C6F4 1b ; 4-C6F5-C6F4 1c ) via fluoride transfer to form the complex salts trans-[Ni(iPr2Im)2(solv)(ArF)] FAP (2a-c[solv] ) (solv=Et2O,CH2Cl2,THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh3 , solvent coordination was suppressed and the complexes trans-[Ni(iPr2Im)2(PPh3)(C6F5 )] FAP (trans-2a[PPh3]) and cis-[Ni(iPr2Im)2(Dipp2Im)(C6F5)] FAP (cis-2a[Dipp2Im]) (Dipp2Im=1,3-bis(2,6-di-iso -propylphenyl)-imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp2Im)CuF] (3) in CH2Cl2 or 1,2-difluorobenzene led to the isolation of [{(Dipp2Im)Cu}2 ]FAP2 (4). Subsequent reaction of 4 with PPh3 and different carbenes resulted in the complexes [(Dipp2Im)Cu(LB)] FAP (LB = Lewis base) (5a - e ). In the presence of  6Me6, fluoride transfer afforded [(Dipp2Im)Cu(C6Me6)] FAP (5f). The reactivity of 4 demonstrates that it serves as a source of cationic [(Dipp2Im)Cu)]+. Defluorination of Cp2TiF2 (7) resulted in the formation of dinuclear [(F)(Cp)2Ti(μ-F)Ti(Cp)2(F)] FAP (8).