Date of Award

3-6-2024

Publication Type

Thesis

Degree Name

M.Sc.

Department

Chemistry and Biochemistry

Supervisor

Jeremy Rawson

Abstract

Chapter 1 introduces the chemistry of dithiolene complexes including the non-innocent nature of this ligand. Synthetic routes to transition metal complexes, highlighting the oxidative addition chemistry of tetrathiocins are discussed. Their potential applications in fields are described. Chapter 2 explores the oxidative addition of bis(4, 5-dimethoxybenzo)-1,2,5,6-tetrathiocin, (dmobdt)2, to zero-valent Ni(COD)2 under microwave conditions is sensitive to the nature of phosphine co-ligands present. Previous, reaction of Ni(COD)2 with the chelating phosphine, dppe, was shown to afford the square planar Ni(II) complex Ni(dmobdt)(dppe) (1, Figure 1).1 This chapter studies the role of phosphines (dppm, dppe, and dppp) in modifying the outcome of the reaction chemistry. In some reactions the complex, Ni(dmobdt)2 (2), was isolated as one of two Ni products. The crystal structure and electronic structure of 2 is described as a representation of complexes 1-3. The crystal structure and electronic structure of 4 is discussed. Chapter 3 reports the collection of cyclopentadienyl metal dithiolenes synthesized with varying metal centers, Fe, V, and Mo by the oxidative addition of the bis(4, 5-dimethoxybenzo)-1,2,5,6-tetrathiocin, (dmobdt)2, the tetrathiocin held constant throughout the two chapters. This section tells the story of structural differences of the three metals and supports the coordination of the chelating dithiolene ligand. The geometries of the complexes are dependant on the electronic configuration of the metal centers. Chapter 4 summarizes the oxidative addition chemistry of tetrathiocins to the transition metals that have been a focused on, in the Rawson group. This chapter concludes the findings of the two projects of this thesis and discusses possible future works that may be undertaken by the Rawson group

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