NHC-Copper(I) Main Group Complexes for Synthesis and Catalysis

  • Thomas Horsley Downie

Student thesis: Doctoral ThesisPhD


In 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 Award22 Jun 2022
Original languageEnglish
Awarding Institution
  • University of Bath
SupervisorDavid Liptrot (Supervisor) & Michael Hill (Supervisor)

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