Rethinking calcium fluoride chemistry: from structural and mechanistic studies to applied methodologies

Thesis

The research in this thesis centres around an overarching theme of rethinking (nucleophilic) fluoride chemistry. It has been carried out at the interface between fundamental- and application-driven science, and brings together key themes from organic and inorganic chemistry, with strong mechanistic emphasis. Little fundamental understanding of the reactivity of Ca–F moieties is available to guide methodology development to use CaF₂ directly with well-defined molecular species containing Ca–F bonds being extremely rare. Furthermore, existing examples are strongly aggregated and evidence no nucleophilic fluoride delivery. Here, accessible structural motifs have been expanded to include monomeric complexes (unlocking the first examples of nucleophilic delivery) and terminal Ca–F systems, resulting in the first calcium-catalysed fluorination. Systematic control of fluoride lability proved crucial in this system, a theme also central to the development of the first catalytic Appel-type fluorination, which exploits a phosphorus-based delivery vehicle.

Authors: Struijs, JJC

• DOI: 10.5287/ora-qygbgjkwo
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: inorganic chemistry; organic chemistry; fluoride; calcium; mechanism
• Subjects: Chemistry