The element fluorine is becoming increasingly pervasive in modern life. It is commonly incorporated
into pharmaceutical and agrochemical compounds, inert materials, polymers, refrigerant gases,
aerosols and electrolytes amongst other applications. But the current fluorine industry has three
major problems. These are: the dwindling supply of fluoride containing mineral resources; the safety
and practicality concerns of handling toxic fluorinating or hydrofluorinating agents; and the
environmental impacts of many ‘single-use’ fluorinated products. The development of fluorine (F2),
fluoride (F-) and hydrogen fluoride (HF) transfer technologies can alleviate all three of these key issues
through the formation of a fluorine cycle.
Within this thesis, three new catalytic systems for the transfer of fluoride or hydrogen fluoride
between organic substrates are presented. The systems cover the fluoride metathesis of
perfluoroarenes with carbonyl derivatives; the hydrofluorination of alkynes through the reaction of
perfluoroarenes with protic nucleophiles and the shuttling of hydrogen fluoride between
fluoroalkanes and alkynes. For each system a scope of substrates is presented along with mechanistic
insights through kinetic analysis and computational modelling (DFT). This work represents a proof of
principle that will hopefully aid the future development of fluorine recycling technologies that are
necessary for the future sustainability of the fluorine industry.