The first chapter is an introduction to the development of carbon-hydrogen bond, (C-H), activation. The use of acidic solvents for C-H activation is addressed, and catalyst inhibition by water or methanol is discussed as one of the major problems in creating active catalysts. New approaches for designing C-H activation/functionalization catalysts that operate in water are discussed.

Chapter two is the study of an electron rich platinum complex, Pt(NNC)TFA where NNC = 6-phenyl-4,4'-di-tert-butyl-2,2'-bipyridine and TFA = trifluoroacetate, designed to overcome the water inhibition of the Pt(bipyrimidine)Cl ₂ catalyst. The mechanism for the H/D exchange between benzene and trifluoroacetic acid is studied using this catalyst. The energetics for C-H activation (both coordination and cleavage of the C-H bond) by the Pt(bipyrimidine)(TFA) ₂ complex and the Pt(NNC)TFA complex are calculated and compared by DFT.

Chapter three is the synthesis and reactivity of a water soluble cyclometallated (NNC)Ir(OH)₂Py complex that is competent for the H/D exchange of benzene and water. This complex was insoluble in water at elevated temperatures (150°C), which hindered its use as a catalyst. To overcome the insolubility in water at elevated temperatures, I designed water soluble (NNC derivatives) ligands. Several of these water soluble iridium complexes were synthesized and tested. Further work is ongoing in this area to determine if there is a pH dependence on rate of C-H activation using these catalysts.

Chapter 4 is a collection of related work. The first section is the synthesis of a water soluble cyclometallated bisphenylpyridine iridium μ-OH bridged dinuclear complex. This complex is being synthesized for the C-H activation of hydrocarbons in basic aqueous media and to gain further understanding about μ-hydroxo bridged dinuclear complexes. The second section contains DFT calculations of an iridium(I) bipyridine hydroxo aquo complex for the C-H activation of hydrocarbons in water. Protonation of the electron rich iridium(I) center by water is found to be highly exothermic, which results in a ground state stabilization. Calculations were also performed on Goldberg's cyclometallated (PNP) iridium hydroxo complex, and the protonation by water is calculated to be endothermic. Lastly, a sterically hindered NNC ligand is synthesized. Attempts have been made to cyclometallate it to iridium for the purpose of generating a five coordinate complex that could show interesting chemistry.