Modeling Transition Metal Catalysts for Small Molecule Activation and Functionalization

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There is a high demand for the development of processes for the conversion of ubiquitous molecules into industrially useful commodities. Transition metal catalysts are often utilized for the activation and functionalization of small organic molecules due to their diverse nature and proven utility with a myriad of chemical transformations. The functionalization of methane (CH4) and dinitrogen (N2) to methanol (CH3OH) and ammonia (NH3) respectively is of particular interest; however, both methane and dinitrogen are essentially inert due to the inherit strength of their bonds. In this dissertation a series of computational studies is performed to better understand the fundamental chemistry … continued below

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Figg, Travis M. May 2013.

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  • Figg, Travis M.

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There is a high demand for the development of processes for the conversion of ubiquitous molecules into industrially useful commodities. Transition metal catalysts are often utilized for the activation and functionalization of small organic molecules due to their diverse nature and proven utility with a myriad of chemical transformations. The functionalization of methane (CH4) and dinitrogen (N2) to methanol (CH3OH) and ammonia (NH3) respectively is of particular interest; however, both methane and dinitrogen are essentially inert due to the inherit strength of their bonds. In this dissertation a series of computational studies is performed to better understand the fundamental chemistry behind the functionalization of methane and the activation of dinitrogen in a homogeneous environment. A catalytic cycle is proposed for the oxy-functionalization of methane to methanol. The cycle consists of two key steps: (1) C-H activation across a metal-alkoxide bond (M-OR), and (2) regeneration of the M-OR species through an oxy-insertion step utilizing external oxidants. The C-H activation step has been extensively studied; however, the latter step is not as well understood with limited examples. For this work, we focus on the oxy-insertion step starting with a class of compounds known to do C-H activation (i.e., Pt(II) systems). Computational studies have been carried out in an attempt to guide experimental collaborators to promising new systems. Thus, the majority of this dissertation is an attempt to extend transition metal mediated C-O bond forming reactions to complexes known to perform C-H activation chemistry. The last chapter involves a computational study of the homogeneous cleavage of N2 utilizing iron-?-diketiminate fragments. This reaction has been studied experimentally, however, the reactive intermediates were not isolated and the mechanism of this reaction was unknown. Density functional theory (DFT) calculations are carried out to elucidate the mechanism of the reductive cleavage of N2 via the sequential addition of iron- ?-diketiminate fragments to N2 to form a bis-nitride (N3-) intermediate. The role of potassium promoters on the dinitrogen and bis-nitride species is also investigated.

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  • May 2013

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  • Feb. 1, 2014, 6:14 p.m.

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  • April 28, 2020, 12:48 p.m.

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Figg, Travis M. Modeling Transition Metal Catalysts for Small Molecule Activation and Functionalization, dissertation, May 2013; Denton, Texas. (https://digital.library.unt.edu/ark:/67531/metadc271814/: accessed May 27, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .

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