Fluoride abstraction from different types of transition metal fluoride complexes [L_nMF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C₂F₅)₃PF₂ to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C₂F₅)₃PF₃]⁻) is reported. (C₂F₅)₃PF₂ reacted with trans‐[Ni(iPr₂Im)₂(Ar^F)F] (iPr₂Im=1,3‐diisopropylimidazolin‐2‐ylidene; Ar^F=C₆F₅, 1 a; 4‐CF₃‐C₆F₄, 1 b; 4‐C₆F₅‐C₆F₄, 1 c) through fluoride transfer to form the complex salts trans‐[Ni(iPr₂Im)₂(solv)(Ar^F)]FAP (2 a‐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‐2 a[PPh₃]) and cis‐[Ni(iPr₂Im)₂(Dipp₂Im)(C₆F₅)]FAP (cis‐2 a[Dipp₂Im]) (Dipp₂Im=1,3‐bis(2,6‐diisopropylphenyl)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]²⁺2 FAP⁻ (4). Subsequent reaction of 4 with PPh₃ and different carbenes resulted in the complexes [(Dipp₂Im)Cu(LB)]FAP (5 a–e, LB=Lewis base). In the presence of C₆Me₆, fluoride transfer afforded [(Dipp₂Im)Cu(C₆Me₆)]FAP (5 f), which serves as a source of [(Dipp₂Im)Cu)]⁺. Fluoride abstraction of [Cp₂TiF₂] (7) resulted in the formation of dinuclear [FCp₂Ti(μ‐F)TiCp₂F]FAP (8) (Cp=η⁵‐C₅H₅) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.

中文翻译：

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三(五氟乙基)二氟正膦：过渡金属化学的多功能氟化物受体

通过路易斯酸三(五氟乙基)二氟正膦(C ₂ F ₅ ) ₃ PF ₂从不同类型的过渡金属氟化物络合物[L _n MF] (M=Ti, Ni, Cu)中提取氟化物，生成阳离子过渡金属络合物报道了三(五氟乙基)三氟磷酸盐抗衡离子( FAP阴离子，[(C ₂ F ₅ ) ₃ PF ₃ ] ^{- )。}(C ₂ F ₅ ) ₃ PF ₂与反式-[Ni( i Pr ₂ Im) ₂ (Ar ^F )F] ( i Pr ₂ Im=1,3-二异丙基咪唑啉-2-亚基; 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 ) 通过氟化物转移形成复合盐trans -[Ni( i Pr ₂ Im ) ₂ (solv)(Ar ^F )] FAP ( 2 a - c[solv] ; solv=Et ₂ O, CH ₂ Cl ₂ , THF) 取决于反应介质。_{在较强的路易斯碱（如卡宾或 PPh 3 ）}存在下，溶剂配位受到抑制，配合物trans ‐[Ni( i Pr ₂ Im) ₂ (PPh ₃ )(C ₆ F ₅ )] FAP ( trans ‐2 a[ PPh ₃ ] ) 和cis ‐[Ni( i Pr ₂ Im) ₂ (Dipp ₂ Im)(C ₆ F ₅ )] FAP ( cis ‐2 a[Dipp ₂ Im] ) (Dipp ₂ Im=1,3‐bis分离出(2,6-二异丙基苯基)咪唑啉-2-亚基)。在 CH ₂ Cl _{2或 1,2-二氟苯中从 [(Dipp 2} Im)CuF] ( 3 ) 中提取氟化物，从而分离出 [{(Dipp ₂ Im)Cu} ₂] ²⁺ 2  FAP ^- ( 4 )。随后4与 PPh ₃和不同的卡宾反应生成了配合物 [(Dipp ₂ Im)Cu(LB)] FAP ( 5 a – e , LB=路易斯碱)。_{在C 6} Me ₆存在下，氟化物转移得到[(Dipp ₂ Im)Cu(C ₆ Me ₆ )] FAP ( 5 f )，其充当[(Dipp ₂ Im)Cu)] ⁺的来源。_{[Cp 2} TiF ₂ ] ( 7 )的氟化物提取导致形成具有一个末端氟化物的双核 [FCp ₂ Ti(μ‐F)TiCp ₂ F] FAP ( 8 ) (Cp=η ⁵ ‐C ₅ H ₅ )每个钛原子上有一个配体和一个额外的桥联氟化物配体。