Nickel Perfluoroalkyl Complexes Supported by Simple Acetate Coligands.

The interaction of tetramethylammonium acetate with [(MeCN) 2 Ni(CF 3 ) 2 ], [(MeCN) 2 Ni(C 2 F 5 ) 2 ], and [NMe 4 ][(MeCN)Ni(CF 3 ) 3 ] was explored by 19 F NMR spectroscopy. We show that depending on the nature of the nickel complex, one or two acetate ligands can add to the metal center and replace the nickel-bound MeCN ligands, depending on the acetate concentration. The number of acetates that could bind to nickel, and whether the resulting complex exists as a monomer or dimer, was determined to be dependent on the nature of the fluoroalkyl ligand. Moreover, we observe that oxidation of the nickel center of [(MeCN) 2 Ni(CF 3 ) 2 ] in the presence of two equivalents of acetate leads cleanly to the octahedral, paramagnetic (EPR spectroscopy), and anionic Ni(III) complex [NMe 4 ][Ni(CF 3 ) 2 (OAc) 2 ].