The influence of dynamic coordination spheres in metal-based homogeneous catalysis

Vladimirov, Vladimir 2024. The influence of dynamic coordination spheres in metal-based homogeneous catalysis. PhD Thesis, Cardiff University. Item availability restricted.

Preview	PDF (Thesis) - Accepted Post-Print Version Download (18MB) | Preview
	PDF (Cardiff University Electronic Publication Form) - Supplemental Material Restricted to Repository staff only Download (133kB)

Abstract

This thesis features two distinct "case studies" that fall under the umbrella of homogeneous catalysis, and where the concept of dynamic coordination sphere could be involved. A combination of laboratory and computational studies has been conducted to attempt to devise metal-based catalysts for these reactions and gain insights into their mechanisms and the role of the dynamic coordination sphere. Chapter 2 of this thesis focuses on the ring-opening copolymerisation of epoxides and cyclic anhydrides, which results in polyester molecules. The literature provides multiple examples of catalysts based on various metals, but Chapter 2 considers a potential candidate in a novel indium complex, which was found to be active towards ring-opening co-polymerisation in conjunction with a [PPN]Cl co-catalyst, with improved polydispersities observed compared to just the co-catalyst alone. Computational studies were also conducted to examine the propagation cycle of the reaction. In chapter 3 of this thesis, a series of novel stereogenic-at-metal complexes of ruthenium, rhodium, and iridium is presented. Simple and commercially available 3-amino-1-azacycle ligands were found to effect complete diastereomeric selectivity in the synthesis of these complexes. The complexes can facilitate the transfer hydrogenation of aromatic ketones, but, unfortunately, no stereoselectivity was observed. Nevertheless, this represents an interesting addition to the transfer hydrogenation literature, and these complexes could potentially catalyse the transfer hydrogenation of other unsaturated compounds. Computational studies were also conducted to gain mechanistic insight into the catalytic process, as well as to investigate the diastereoselectivity observed in the synthesis of the complexes

Item Type:	Thesis (PhD)
Status:	Unpublished
Schools:	Schools > Chemistry
Date of First Compliant Deposit:	17 April 2025
Last Modified:	24 Apr 2025 10:18
URI:	https://orca.cardiff.ac.uk/id/eprint/177773

Actions (repository staff only)

Edit Item