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Easy Access to the Copper(III) Anion [Cu(CF 3 ) 4 ] −
Author(s) -
Romine Andrew M.,
Nebra Noel,
Konovalov Andrey I.,
Martin Eddy,
BenetBuchholz Jordi,
Grushin Vladimir V.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201411348
Subject(s) - chemistry , isomerization , copper , crystallography , ion , atom (system on chip) , x ray crystallography , crystal structure , ligand (biochemistry) , yield (engineering) , inorganic chemistry , diffraction , catalysis , materials science , organic chemistry , biochemistry , physics , receptor , computer science , optics , metallurgy , embedded system
CuCl or pre‐generated CuCF 3 reacts with CF 3 SiMe 3 /KF in DMF in air to give [Cu(CF 3 ) 4 ] − quantitatively. [PPN] + , [Me 4 N] + , [Bu 4 N] + , [PhCH 2 NEt 3 ] + , and [Ph 4 P] + salts of [Cu(CF 3 ) 4 ] − were prepared and isolated spectroscopically and analytically pure in 82–99 % yield. X‐ray structures of the [PPN] + , [Me 4 N] + , [Bu 4 N] + , and [Ph 4 P] + salts were determined. A new synthetic strategy with [Cu(CF 3 ) 4 ] − was demonstrated, involving the removal of one CF 3 − from the Cu atom in the presence of an incoming ligand. A novel Cu III complex [(bpy)Cu(CF 3 ) 3 ] was thus prepared and fully characterized, including by single‐crystal X‐ray diffraction. The bpy complex is highly fluxional in solution, the barrier to degenerate isomerization being only 2.3 kcal mol −1 . An NPA study reveals a huge difference in the charge on the Cu atom in [Cu(CR 3 ) 4 ] − for R=F (+0.19) and R=H (+0.46), suggesting a higher electron density on Cu in the fluorinated complex.