Complexes of Schiff-base macrocycles and donor-expanded dipyrrins for catalysis and uranyl reduction
Pankhurst, James Richard
The modern world faces a number of challenges related to energy and the environment. Atmospheric levels of carbon dioxide have now surpassed the 400 ppm mark due to the burning of fossil fuels, yet despite its abundance and potential use as a C1 feedstock for value-added products, there are both thermodynamic and kinetic barriers associated with the strong carbon-oxygen bonds that preclude its widespread deployment in industry. Nuclear energy is an alternative power source that reduces carbon emissions by billions of tonnes each year, but there are widespread concerns regarding the treatment of the radioactive waste that it accrues (of which the main component is uranyl, [UO2]2+). Most of the work presented in this thesis concerns the synthesis of transition-metal complexes, with the aim of directing catalytic reactivity to convert CO2 to useful products. Part of this thesis also concerns the synthesis of uranyl complexes and the study of uranyl reduction chemistry, which is relevant to uranyl remediation and nuclear waste treatment at a fundamental level. Making use of Earth-abundant metals to carry out hydrocarbon oxidation catalysis is a further focus of this work, as the efficient production of oxygenated compounds under mild conditions is of importance to the fine-chemical industry. Chapter 1 reviews important complexes reported in the literature that successfully convert CO2 to useful products through molecular, homogenous electro-catalysis and ring-opening copolymerisation catalysis. Reactions that exemplify a two-electron reduction of uranyl (i.e. uranium(VI) to uranium(IV)) are reviewed, along with uranyl complexes that undergo ligand-centred redox to give ligand-based radicals. The state of the literature on hydrocarbon oxidation catalysis is reviewed in the introduction. The development of multinuclear, macrocyclic complexes and the reactivity of dinuclear Pacman complexes are also presented. Chapter 2 reports the synthesis and characterisation of a new set of Schiff-base macrocycles and acyclic dipyrrin ligands. A number of attempted synthetic routes towards incorporating a dipyrrin coordination compartment in a macro-cyclic setting are discussed. Differences in electronic structures between dipyrromethanes and dipyrromethenes are also examined by theoretical and experimental methods. Chapter 3 introduces the coordination chemistry of these new macrocycles with zinc(II), where the isolation of dinuclear and tetranuclear complexes is demonstrated using different zinc(II) precursors. Tetranuclear zinc-alkyl complexes presented here are shown to be resistant to insertion chemistry with small molecules, but readily form zinc-oxo, -hydroxyl and -alkoxide clusters upon protonolysis with water and alcohols. These molecular clusters display reactivity towards CO2: a zinc-hydroxyl complex precipitates ZnCO3 at high temperature; and zinc-alkoxide complexes have been used to catalyse the copolymerisation reaction between CO2 and cyclohexene oxide to form polycarbonates. Chapter 4 describes the synthesis of late-transition-metal complexes of macrocyclic ligands and dipyrrins, and explores the relationship between macrocycle geometry and electronic structure. Their reactivities towards CO2 are assessed here, using cyclic voltammetry to assess the electro-catalytic activity of a number of the complexes. Chapter 5 reports the oxidation chemistry of hydrocarbon substrates catalysed by copper(II) complexes. High-temperature catalysis occurs with bimetallic copper(II) complexes, and this chapter describes how added FeCl3 acts as a co-catalyst, leading to greater catalyst stability and allowing the catalytic reaction to occur at room temperature. A range of analytical methods have been used to deduce the catalytically active species, and chemical kinetic measurements have been used to deduce a possible reaction mechanism. Chapter 6 reports the synthesis of a uranyl(VI) dipyrrin complex and details characterisation of its electronic structure by theoretical and experimental methods. Theoretical modelling has indicated that the observed two-electron reduction of uranium(VI) to uranium(IV) is facilitated by the dipyrrin ligand, representing a novel uranyl reduction mechanism.