Physicochemical and structural studies of ferrocene schiff base derivatives and some associated adducts : a thesis presented in partial fulfilment of the requirements for the degree of Master of Science at Massey University

The results reported in this thesis are an investigation into the synthesis, characterisation, and coordination ability of some new Schiff base ferrocenyl derivatives. Chapter One gives a brief overview of the practical applications that ferrocene based compounds have been put to, since ferrocenes first synthesis in 1951. Chapter Two outlines the preparation and characterisation of six new Schiff base ferrocenyl derivatives, along with a new synthesis and full characterisation of a ferrocenyl thiosemicarbazide derivative which was first synthesised in 1968. The X-ray structure of bis-N-(0-hydroxybenzylidene) ferrocenylimine,(L11), was established, showing relatively strong intramolecular hydrogen bonding between the Schiff base nitrogen and the hydrogen of the hydroxy group on the phenol. In Chapter three reduction attempts of the ferrocene derivatives in Chapter 2 are reported. The synthesis and characterisation of a borane adduct of the N-(o-hydrazonylpyridine) ferrocenimine ligand, (L2.BH3 ), is studied. Its single crystal X-ray structure is determined and the adduct is compared to the parent L2 ligand. Chapter Four contains the preparation and characterisation of the complex [Zn(L1)Cl]2 , which is based on the N-(o-hydroxybenzylidene) ferrocenylimine ligand, (L1). Five new metal complexes are reported, [Co(L2)Cl 2 ], [Ni(L2)Br2 ], [Cu(L2)Cl2 ], [Co(L2)Br2 ] and [Zn(L2)Cl2 ] based on the L2 ligand, and these are characterised by mass and infra-red spectroscopies. In Chapter Five the ligands are studied by cyclic voltammetry and Mossbauer spectroscopies, with further cyclic voltammetry studies undertaken on the complexes. The electrochemical oxidation trends observed in the cyclic voltammetry studies on the Schiff base derivatives are in parallel with the Mossbauer studies, which have the results rationalised in terms of electron population movements within the 57 Fe d-orbitals and the p-orbitals of the cyclopentadienyl rings