| Summary: | <p>As a reliable, convenient, and advantageous tool in the theoretical investigations of
bioorganic, inorganic, and organometallic chemistry, density functional theory (DFT)
computations have provided chemists with numerous significant insights. The
understanding of mechanisms of chemical reactions, and the design and development of
catalysts have been greatly promoted by the employment of DFT.</p>
<p>In this dissertation, the applications of DFT computations in the catalytic bioorganic, inorganic, and organometallic systems were studied. Phosphoramidate hydrolysis catalyzed by human histidine triad nucleotide binding protein 1 (hHint1) was investigated using a cluster-model DFT approach, and the key involvement of the histidine triad as a proton shuttle was discussed in the proposed mechanism. The IEFPCM-Bondi-B3LYP/BS1 methodology was demonstrated as a reliable, and time-saving model in computing the reduction potentials of transition metal complexes. Moderate accuracy (MAD = 0.233 V, mean absolute deviation) and good linear correlation (R<sup>2</sup> = 0.93) between computed and experimental reduction potentials of the 49 studied species are osberved. The fluxionality of cyclohexenyl manganese tricarbonyl [(C<sub>6</sub>H<sub>9</sub>)Mn(CO)<sup>3</sup>] was
investigated using DFT computations, which uncovered a previously uncharacterized
closed <i>C</i>s agostomer. The intramolecular oxidative amination of an alkene catalyzed by
the extreme π-loading N-heterocyclic carbene pincer Tantalum(V) bis(imido) complex was
also computationally analyzed, and the mechanisms of the formation of oxidative
amination product, reduction product, and hydroamination product were investigated. The
computational results are consistent with the experimentally observed product ratios and
selectivity.</p>
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