The synthesis, characterization and reactivity of high oxidation state nickel fluorides

Abstract

The research described in this thesis has mainly addressed the challenge of the synthesis of thermodynamically unstable nickel fluorides, which cannot be made by traditional thermal methods. A low-temperature approach towards the synthesis of such transition metal fluorides exploits the greater thermodynamic stability of high oxidation states in anions and involves the use of anhydrous hydrogen fluoride (aHF) as a solvent. The general method consists of combining an aHF soluble starting material (e.g., K{sub 2}NiF{sub 6}) with a Lewis fluoroacid (e.g., BF{sub 3}), which precipitates a neutral polymeric solid state fluoride: 2 K{sup +} + NiF{sub 6}{sup 2{minus}} + BF{sub 3} {r_arrow} NiF{sub 4} + 2 BF{sub 4}{sup {minus}} + 2 K{sup +}. At room temperature, this reaction yields a different structural phase, with composition K{sub x}NiF{sub 3} (x {approx} 0.18). This material has a pseudo-hexagonal tungsten bronze structure (H{sub 0}-K{sub x}NiF{sub 3}), and is an ionic conductor, probably due to K{sup +} ions hosted in the lattice channels. R-NiF{sub 3} is capable of fluorinating a wide range of inorganic and organic substrates. These reactions have probably shed light on the mechanism of the Simons Electrochemical Fluorination (ECF) Process, an important industrial method of fluorinating organic compounds. It has long been speculated that NiF{sub 3} plays a role in the ECF process, which uses nickel electrodes in aHF solvent. K{sub 2}NiF{sub 6} also fluorinates organic compounds in aHF, but interestingly, yields different fluorinated products. The reduction of R-NiF{sub 3} and K{sub 2}NiF{sub 6} during fluorination reactions yields NiF{sub 2}. A method has been developed to regenerate NiF{sub 6}{sup 2{minus}} from NiF{sub 2}.