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Title: Inexpensive methods of catalytic hydrophosphination utilising iron and simple metal salts
Author: Gallagher, Kimberley
Awarding Body: University of Bath
Current Institution: University of Bath
Date of Award: 2019
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This thesis details the development of iron-based catalysts for the hydrophosphination of unsaturated compounds. Conditions were optimised for each process and the substrate scope was established. Experimental and spectroscopic studies were used to investigate the mechanism of the hydrophosphination of styrene. Chapter 1 gives an overview of hydrophosphination, both stoichiometric and catalytic, focusing on the reactions of iron. The value of these hydrophosphination products is discussed. Chapter 2 details the catalytic hydrophosphination to form unusual terminally substituted phosphines using both Fe(HMDS)2THF and KHMDS respectively. Chapter 3 Shows that by introduction of a simple salen ligand to an iron catalysed system gave room temperature reactivity at very low catalyst loadings. Only 0.5 mol% pre-catalyst was required for the room temperature synthesis of a variety of phosphines through hydrophosphination. Further, this work explored the use of an iron-porphyrin μ-oxo catalyst for a range of similar products. Hyrophosphination with phenylphosphine is outlined, wherein a single addition is seen to take place thermally. Chapter 4 outlines kinetic and mechanistic aspects of catalytic hydrophosphination with iron(salen)-μ-oxo. A Hammett study was conducted for a variety of functional groups on the alkene substrate concluding that there was a change in the rate determining step moving from electron withdrawing to electron donating groups. This work culminated in the publication of two papers in impactful peer reviewed journals.
Supervisor: Webster, Ruth ; Whittlesey, Michael Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Iron ; Hydrophosphination ; Catalysis ; Phosphine ; Salen