Preliminary NMR data indicate that a new platinum compound, assigned (TpyO)PtMe (TpyO = 2,6-bis-(2’pyridyl)-4-pyridonate), can be synthesized by the addition of impure trans-(DMSO)2PtMeCl to impure 2,6-bis(2’-pyridyl)-4-hydroxypyridine (TpyOH) in the presence of NEt3 in about 10% yield. It is likely that the yield could be increased by using purified TpyOH and (DMSO)2PtMeCl. The metalation step of the synthesis was also attempted using (COD)PtMeCl but was unsuccessful with either Na2CO3 or NEt3 as bases, most likely due to the chelate effect of the bidentate COD. Future work with (TpyO)PtMe will include the addition of H+/D+ to generate the platinum (IV) complex, [(TpyO)Pt(Me)(H)]+, and/or the σ-complex [(TpyO)Pt(Me-H)]+ in order to examine the kinetic, isotope, and thermodynamic effects of the resulting reductive elimination reaction.

Our country continues to demand clean renewable energy to meet the growing energy needs of our time. Thus, natural gas, which is 87% by volume of methane, has become a hot topic of discussion because it is a clean burning fuel. However, the transportation of methane is not easy because it is a gas at standard temperature and pressure. The usage of transition metals for the conversion of small organic species like methane into a liquid has been a longstanding practice in stoichiometric chemistry. Nonetheless, the current two-step process takes place at a high temperature and pressure for the conversion of methane and steam to methanol via CO + H2 (syngas). The direct oxidation of methane (CH4) into methanol (CH3OH) via homogeneous catalysis is of interest if the system can operate at standard pressure and a temperature less than 250 C. Methane is an inert gas due to the high C-H bond dissociation energy (BDE) of 105 kcal/mol. This dissertation discusses a series of computational investigations of oxy-insertion pathways to understand the essential chemistry behind the functionalization of methane via the use of homogeneous transition metal catalysis. The methane to methanol (MTM) catalytic cycle is made up of two key steps: (1) C-H activation by a metal-methoxy complex, (2) the insertion of oxygen into the metal−methyl bond (oxy-insertion). While, the first step (C-H activation) has been well studied, the second step has been less studied. Thus, this dissertation focuses on oxy-insertion via a two-step mechanism, oxygen-atom transfer (OAT) and methyl migration, utilizing transition metal complexes known to activate small organic species (e.g., PtII and PdII complexes). This research seeks to guide experimental investigations, and probe the role that metal charge and coordination number play.