AbstractIn the last two decades, NHC-copper(I) main group complexes have emerged as powerful synthetic tools able to facilitate a vast array of organic transformations. Nonetheless, some subsets of this class of compounds, and catalytic transformations that they can mediate, require further investigation. Chapter 1 introduces the chemistry in this thesis, placing it in context by describing the synthesis and reactivity of NHC-copper(I) main group complexes already present in the literature.
The use of NHC-copper(I) hydride complexes in mediating a new catalytic route to the generation of phosphanes is described Chapter 2. Chapter 3 then examines the synthesis and reactivity of a series of NHC-copper(I) phosphides, with characterisation of the products that resulted from insertion reactions with a series of unsaturated compounds. Phosphane generation and insertion reactivity are then combined in a study of catalytic hydroelementation reactions of heterocumulenes, mediated by NHC-copper(I) complexes.
The synthesis of a stable copper(I) boryl complex bearing a ring-expanded NHC is described in Chapter 4. The reactivity of this compound with heterocumulenes resulted in the assembly of a series of heterocyclic ring systems, coordinated to the NHC-copper(I) scaffold. The complex and varying mechanistic pathways by which these new compounds are formed were examined.
Chapter 5 reports the catalytic formation of P–P bonds by reduction of P–O bonds, mediated by NHC-copper(I) complexes. Mechanistic investigations suggested that this proceeds via the generation of NHC-copper(I) main group complexes described in the earlier chapters of this thesis. Kinetic studies were undertaken to provide insight into this unprecedented catalytic mechanism.
|Date of Award||22 Jun 2022|
|Supervisor||David Liptrot (Supervisor) & Michael Hill (Supervisor)|