Marshall, Jane E.; (1992) The chemistry of ligands derived from hydrogen sulphide or thiols with transition metals. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

Chapter One contains a literature survey of the chemistry of sulphur and sulphur- containing ligands with transition metal complexes. The survey begins with the chemistry of one metal centre progressing to two, three and above, with sulphur ligands. The formation, characterisation and structure of the complexes is included. Chapter Two concerns the chemistry of ruthenium phosphine complexes. The chapter is introduced by an explanation of the trans influence and trans effect, and the discussion progresses to the use of this effect in the synthesis of ruthenium aqua and acetonitrile complexes. Their further reaction giving a tetrakisphosphine complex is discussed, crystal structure determined, and it's unusual 1H NMR spectrum is explained using anisotropic considerations. The chemistry of an iridium-phosphine complex reacting with hydrogen sulphide or two other thiols is discussed in Chapter Three. This includes their synthesis and characterisation using X-ray crystallography, 1H NMR and mass spectroscopies. Crystallographic data from this Chapter and Chapter Two are discussed, as are attempts to react the complexes as 'Inorganic Thiols'; to form larger complexes by oxidation or reaction with metal centres. Chapter Four contains the reactions of the same iridium-phosphine complex with selenium-containing reagents to synthesise analogues of the 'inorganic thiol' complexes. The 1H NMR spectra are discussed as are 1H NMR experiments carried out to determine; the effect of light on these and the 'inorganic thiol' complexes, and to follow their protonation. Chapter Five contains the reactions of hydrogen sulphide and various mono- and dithiols with palladium complexes. This includes a different route in the synthesis of trinuclear complexes, and the formation of polymeric thiolate complexes are discussed including their further reaction to form mononuclear palladium thiolate phosphine complexes. These are characterised by NMR and mass spectroscopies and X-ray crystallography.

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