Abstract
Since the early 2000s, a new generation of low oxidation main group chemistry has flourished, exemplified by the report of a magnesium(I) dimer in 2006 and an aluminyl anion in 2018. These have allowed the isolation of new and exciting element-element bonds and facilitated exotic chemical transformations; these species have the potential to manipulate other elements into behaving in ways at odds with their expected reactivity.Chapter 1 focuses on three areas pertinent to the work reported in this thesis. Firstly, the development of a new class of low oxidation aluminium complexes, aluminyl anions. Secondly, the development of NHCcopper(I) main group compounds and their reactivity, which is dominated mostly by the Cuδ+– Eδ− bond polarity. Finally, the isolation of a magnesium(I) dimer and the generation of new magnesium-metal bonded species is summarised.
Chapter 2 details the synthesis and characterisation of two aluminium halide species, supported by two monodentate amide ligands, potentially capable of undergoing reduction to form an acyclic aluminyl anion.
Chapter 3 follows the successful reduction, and the characterisation of a potassium bridged acyclic aluminyl anion, along with its reactivity towards s- and p-block electrophiles.
Chapter 4 reports the synthetic route towards an isolable NHC supported copper-magnesium bimetallic complex. Along with the full structural characterisation of this species, quantum chemical calculations proposed a bond polarisation of Cuδ−–Eδ+, suggesting this species could act as a source of the nucleophilic synthon [(NHC)Cu]−.
Chapter 5 focuses on demonstrating this nucleophilic ability experimentally with a host of s-, d- and p-block electrophiles.
| Date of Award | 25 Jun 2025 |
|---|---|
| Original language | English |
| Awarding Institution |
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| Supervisor | David Liptrot (Supervisor) & Ruth Webster (Supervisor) |
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