Syntheses of diphosphine gold (I) complexes from gold THT and two ligands, 4, 5-bis (diphenylphosphino)-4-cyclopenten-1, 3-dione (BPCD) and 2,3-bis(diphenylphosphino)-N-phenylmaleimide (BPPM), were done separately. The reactions happened under ice conditions followed by room temperature conditions and produced two diphosphine gold (I) complexes in moderated yield. Spectroscopic results including nuclear magnetic resonance (NMR) and X-ray crystallography were used to study and determine the structures of the products formed. Moreover, X-rays of all newly synthesized diphosphine gold (I) complexes were compared with the known X-ray structures of other phosphine and diphosphine gold (I) complexes. There were direct resemblances in terms of bond length and angle between these new diphosphine gold (I) complex structures and those already published. For instance, the bond lengths and angles from the newly prepared diphosphine gold (I) complexes were similar to those already published. Where there were some deviations in bond angles and length between the newly synthesized structures and those already published, appropriate explanation was given to explain the deviation. Heterocyclic ligands bearing acetylacetonate (ACAC) side arm(s) were prepared from ethyl malonyl chloride and the heterocyclic compounds 8-hydroxylquinoline, Syn-2-peridoxyaldoxime, quinoxalinol and 2, 6-dipyridinylmethanol. The products (heterocyclic ACAC ligands) from these reactions were screened with transition metal carbonyl compounds …

Density Functional Theory (DFT) is an effective tool for studying diverse metal systems. Presented herein are studies of a variety of metal systems, which can be applied to accomplish transformations that are currently difficult/impossible to achieve. The specific topics studied utilizing DFT include: 1) C–H bond activation via an Earth-abundant transition metal complex, 2) C–H bond deprotonation via an alkali metal superbase, 3) and amination/aziridination reactions utilizing a CuI reagent. Using DFT, the transformation to methanol (CH3OH) from methane (CH4) was examined. The transition metal systems studied for this transformation included a model FeII complex. This first-row transition metal is an economical, Earth-abundant metal. The ligand set for this transformation includes a carbonyl ligand in one set of complexes as well as a phosphite ligand in another. The 3d Fe metal shows the ability to convert alkyls/aryls to their oxidized counterpart in an energetically favorable manner. Also, “superbasic” alkali metal amides were investigated to perform C—H bond cleavage. Toluene was the substrate of interest with Cs chosen to be the metal of interest because of the highly electropositive nature of this alkali metal. These highly electrophilic Cs metal systems allow for very favorable C—H bond scission with a toluene substrate. …

Density functional theory is an efficient and useful method of solving single-reference computational chemistry problems, however it struggles with multi-reference systems. Modifications have been developed in order to improve the capabilities of density functional theory. In this work, density functional theory has been successfully applied to solve multi-reference systems with large amounts of non-dynamical correlation by use of modifications. It has also been successfully applied for geometry optimizations for lanthanide trifluorides.