Nickel Perfluoroalkyl Complexes Supported by Simple Acetate Coligands.

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Fluorine Chemistry

Background:

• Nickel complexes with fluoroalkyl ligands are important in catalysis and materials science.
• Understanding ligand exchange and redox behavior is crucial for designing new nickel compounds.

Purpose of the Study:

• To investigate the reaction of tetramethylammonium acetate with specific nickel-fluoroalkyl complexes.
• To elucidate the factors controlling acetate ligand addition and complex speciation.
• To explore the oxidation of a nickel complex in the presence of acetate.

Main Methods:

• ¹⁹F NMR spectroscopy was used to monitor the interactions.
• EPR spectroscopy was employed to characterize the paramagnetic Ni(III) complex.

Main Results:

• Acetate ligands replace MeCN ligands on the nickel center, with the number of bound acetates depending on the fluoroalkyl ligand and acetate concentration.
• The formation of monomers or dimers is dictated by the fluoroalkyl ligand.
• Oxidation of [(MeCN)₂Ni(CF₃)₂] with acetate yields the octahedral Ni(III) complex [NMe₄][Ni(CF₃)₂(OAc)₂].

Conclusions:

• The nature of the fluoroalkyl ligand is a key determinant in the coordination chemistry of these nickel complexes.
• The study provides insights into the synthesis and characterization of novel nickel-acetate and nickel(III) complexes.