Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry.
Chemistry
; 27(10): 3504-3516, 2021 Feb 15.
Article
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| MEDLINE
| ID: mdl-33241855
Fluoride abstraction from different types of transition metal fluoride complexes [Ln MF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C2 F5 )3 PF2 to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C2 F5 )3 PF3 ]- ) is reported. (C2 F5 )3 PF2 reacted with trans-[Ni(iPr2 Im)2 (ArF )F] (iPr2 Im=1,3-diisopropylimidazolin-2-ylidene; ArF =C6 F5 , 1 a; 4-CF3 -C6 F4 , 1 b; 4-C6 F5 -C6 F4 , 1 c) through fluoride transfer to form the complex salts trans-[Ni(iPr2 Im)2 (solv)(ArF )]FAP (2 a-c[solv]; solv=Et2 O, CH2 Cl2 , 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(iPr2 Im)2 (PPh3 )(C6 F5 )]FAP (trans-2 a[PPh3 ]) and cis-[Ni(iPr2 Im)2 (Dipp2 Im)(C6 F5 )]FAP (cis-2 a[Dipp2 Im]) (Dipp2 Im=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were isolated. Fluoride abstraction from [(Dipp2 Im)CuF] (3) in CH2 Cl2 or 1,2-difluorobenzene led to the isolation of [{(Dipp2 Im)Cu}2 ]2+ 2 FAP- (4). Subsequent reaction of 4 with PPh3 and different carbenes resulted in the complexes [(Dipp2 Im)Cu(LB)]FAP (5 a-e, LB=Lewis base). In the presence of C6 Me6 , fluoride transfer afforded [(Dipp2 Im)Cu(C6 Me6 )]FAP (5 f), which serves as a source of [(Dipp2 Im)Cu)]+ . Fluoride abstraction of [Cp2 TiF2 ] (7) resulted in the formation of dinuclear [FCp2 Ti(µ-F)TiCp2 F]FAP (8) (Cp=η5 -C5 H5 ) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Chemistry
Asunto de la revista:
QUIMICA
Año:
2021
Tipo del documento:
Article
País de afiliación:
Alemania
Pais de publicación:
Alemania