The synthesis and characterization of new higher nuclearity arene-ruthenium-sulfur clusters : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, New Zealand

Abstract

This thesis describes a project investigating the synthesis and characterization of new higher nuclearity arene-ruthenium-sulfur clusters and arene-ruthenium-nitrogen complexes. The thesis is divided into four chapters, with the introduction in Chapter One. The synthesis and characterization of new higher nuclearity arene-ruthenium-sulfur clusters are described in Chapter Two. These include two novel clusters, [Ru₅S₄(cymene)₄](PF₆)₂, [Ru₄(S₂)(SO)(cymene)₄](PF₆)₂ and one known cluster, [Ru₃S₂(cymene)₃](PF₆)₂. The X-ray crystallographic structures of these three arene-ruthenium-sulfur clusters are discussed in detail including how the number of valence electrons influences the structure, how the solid state structure and single crystal structure effect each other and how the structures determine the chemical shifts and other characters of the clusters. The unusual signals of these three clusters on ¹H NMR spectra are discussed carefully. The mechanisms of formation of arene-ruthenium-sulfur clusters are described in detail. Some electrochemistry and calculations (quantum chemistry) are also involved. The synthesis and characterization of arene-ruthenium-nitrogen complexes are described in Chapter Three. These include two new mono-nuclear complexes, [RuCl₂(NH₃)(cymene)], [Ru(NH₃)₃(cymene)](PF₆)₂, one novel amide dimer [RuCl(NH₂)(cymene)]₂ and one known complex, [RuCl(NH₃)₂(cymene)]PF₆. The mechanisms of reactions in which they are formed are also discussed. In Chapter Four, the experimental data is presented. The X ray crystallography of [Ru₅S₄(cymene)₄](PF₆)₂, [Ru₄(S₂)(SO)(cymene)₄](PF₆)₂, [RuCl₂(NH₃)(cymene)] and [RuCl(NH₂)(cymene)]₂ is described in detail