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Title: σ-Complexes of Copper(I)
Author: Hicken, Alex
ISNI:       0000 0004 7658 7872
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2019
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Three new bent {CuL2} fragments of copper(I) supported by β-diketiminate ligands have been synthesised and characterised in the solid state, in solution and via DFT calculations. The suitability of these {CuL2} fragments to be used as precursors for the formation of σ-complexes with an E-H (E = B) or M-H (M = Zn, Al, Mg, Ca, Au, W) bond has been investigated. Their electronic properties and bent confirmation make them ideal fragments for the stabilisation of σ-complexes of copper(I). A range of σ-complexes of the type Cu-H-E and Cu-H-M (E = B, M = Zn, Al, Mg, Ca, Au) have been isolated and characterised in the solid state, in solution and via DFT calculations. In the case of E = B and M = Zn, Mg and Ca, an insight into their decomposition to 4 coordinate M(Ln)2 species' (Ln = β-diketiminate ligand) has been summarised. Increased Cu---M bond character is observed when the heavier transition metal tungsten is employed, and these complexes can be considered as well defined heterobimetallic hydride species of Cu-H-W. The reactivity of heterobimetallics of the type Cu-H-E and Cu-H-M, whereby E = B and M = Zn, W has been investigated through ligand exchange reactions. σ-Complexes of Cu-H-Au, along with mixtures of isolable group 10 fragments and the gold hydride complex IPrAu-H (IPr = 1,3-di(2,6-diisopropylphenyl)imidazol-2-ylidine), have shown to be selective in the reduction of carbon dioxide to a formate equivalent with HBPin (HBPin = pinacolborane). In summary, this thesis provides new insights into the synthesis, characterisation, stability and reactivity of σ-complexes of copper(I).
Supervisor: Crimmin, Mark Sponsor: Natural Environment Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral