Arene-ruthenium(II) complexes of amines and some biologically important ligands.

This thesis describes some chemistry of [(arene)RuC12]2 complexes and their derivatives, in particular their reactions with biologically important ligands such as amino acids and nucleosides. Chapter 1 reviews the general chemistry of arene-ruthenium compounds from early work by Zelonka and Bennett, to the more recent use of such complexes as catalysts in carbamate reactions. The second part contains a discussion of inorganic complexes as anti cancer agents, in particular those of ruthenium. Chapter 2 describes the preparation and characterisation of a number of arene-ruthenium amine complexes. As previously reported we find that primary amines coordinate whereas tertiary ones do not. However, we report the first examples of secondary amine coordination and the X-ray determination of [(mes)RuCl2(pip)] is described. The reactions of some amino-acids with [(mes)RuCl2]2 are presented in Chapter 3. The resulting complexes, [(mes)RuCl(aa)], are soluble in both water and organic solvents and exist as a pair of diastereomers. A study of the factors influencing the diastereomer ratios was undertaken, including substituting the chloride ligand in the complex [(mes)RuCl(ala)], with a number of other ligands. However, no clear patterns were found for predicting diastereomer ratios. In Chapter 4 the reactions of complexes [(mes)RuCl(L-L)]n+ (L-L = Etmal, Pyr, ala, n= 0; L-L = bipy, n = 1) with carbon monoxide in the presence of AgBF4 are described, and the X-ray structure of [(mes)Ru(CO)(Etmal)]BF4 is reported. The reactions of [(mes)Ru(CO) (Etmal)] BF4 with water and other nucleophiles are described. The final Chapter describes the reactions of [(mes)RuCl2]2 with some nucleobases and theophylline. The molecular structure of the theophylline adduct [(mes)RuCl(H2O) (C7H7N4O2)] is described and it establishes the presence of N(7) coordination. We find the stabilities of the nucleobase complexes to be the same as other metal complexes, with guanosine complexes being the most stable and cytidine ones the least.