A 13C and 6Li variable temperature NMR study of 2-ethylbutyllithium/lithium 2-ethyl-1-butoxide mixed aggregates formed from reacting 2-ethyl-1-butanol with 2-ethylbutyllithium in two O/Li ratios of 0.2/1 and 0.8/1. The 0.2/1 sample resulted in two 2-ethylbutyllithium/lithium 2-ethyl-1-butoxide mixed aggregates and seven lithium hydride/lithium 2-ethyl-1-butoxide mixed aggregates. The lithium hydride mixed aggregates were also studied using selective 1H decoupling experiments. The 0.8/1 sample resulted in six 2-ethylbutyllithium/lithium 2-ethyl-1-butoxide mixed aggregates and five lithium hydride/lithium 2-ethyl-1-butoxide mixed aggregates. A low temperature 13C NMR spectroscopy study of n-pentyllithium indicated three aggregates, most likely a hexamer, an octamer, and a nonamer. A low temperature 13C NMR study of an 0.2/1 O/Li ratio sample of n-pentyllithium mixed with 1-pentanol resulted in three n-pentyllithium/lithium n-pentoxide aggregates mixed aggregates along with the three n-pentyllithium aggregates. 13C NMR data for this mixture gave inconclusive results whether or not lithium hydride/lithium alkoxide mixed aggregates were present in the sample.

An NMR spectroscopy study of trimethylsilylmethyllilthium, TMSM-Li, indicates that TMSM-Li exists as two different aggregates in cyclopentane solution. Using previously reported colligative properties of TMSM-Li in different solutions in connection with new 13C and 6Li NMR data collected in this study, aggregation states were assigned as octamer and hexamer. Low temperature 13C and 6Li NMR peak intensities indicated an equilibrium exists between the two aggregates that shifts toward the octamer as the temperature decreases. ΔH was calculated to be 5.23 + 0.15 kcal/mol and ΔS was calculated to be 17.9 + 0.6 eu for the hexamer/octamer equilibrium system. Samples of TMSM-Li were mixed with TMSM-OH in attempts to form mixed alkyllithium/lithium alkoxide aggregates. 13C NMR data for these mixtures gave inconclusive results whether or not these compounds formed, which is different from other primary alkyllithium compounds studied in the past. A study of neopentyllithium, NpLi, indicates only one aggregate in solution with the aggregation state unknown using low temperature 13C NMR spectroscopy.

One of the main goals of computational methods is to identify reasonable geometries for target materials. Organometallic complexes have been investigated in this dissertation research, entailing a significant challenge based on transition metal diversity and the associated complexity of the ligands. A large variety of theoretical methods have been employed to determine ground state geometries of organometallic species. An impressive number of transition metals entailing diverse isomers (e.g., geometric, spin, structural and coordination), different coordination numbers, oxidation states and various numbers of electrons in d orbitals have been studied. Moreover, ligands that are single, double or triple bonded to the transition metal, exhibiting diverse electronic and steric effects, have been investigated. In this research, a novel de novo scheme for structural prediction of transition metal complexes was developed, tested and shown to be successful.

Glutathione syntethase (GS) is an enzyme that belongs to the ATP-grasp superfamily and catalyzes the second step in the biosynthesis of glutathione. GS has been purified and sequenced from a variety of biological sources; still, its exact mechanism is not fully understood. Four highly conserved residues were identified in the binding site of human GS. Additionally, the G-loop residues that close the active site during catalysis were found to be conserved. Since these residues are important for catalysis, their function was studied computationally by site-directed mutagenesis. Starting from the reported crystal structure of human GS, different conformations for the wild type and mutants were obtained using molecular dynamics technique. The key interactions between residues and ligands were detected and found to be essential for enzyme activity.