Modeling Transition Metal Catalysts for Small Molecule Activation and Functionalization

Modeling Transition Metal Catalysts for Small Molecule Activation and Functionalization

Date: May 2013
Creator: Figg, Travis M.
Description: 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 ...
Contributing Partner: UNT Libraries
Mechanistic Study of Oxy Insertion into Nickel Carbon Bonds with Nitrous Oxide

Mechanistic Study of Oxy Insertion into Nickel Carbon Bonds with Nitrous Oxide

Date: July 5, 2012
Creator: Figg, Travis M. & Cundari, Thomas R., 1964-
Description: Article discussing a mechanistic study of oxy insertion into nickel carbon bonds with nitrous oxide.
Contributing Partner: UNT College of Arts and Sciences
Cooperativity Between Low-Valent Iron and Potassium Promoters in Dinitrogen Fixation

Cooperativity Between Low-Valent Iron and Potassium Promoters in Dinitrogen Fixation

Date: June 26, 2012
Creator: Figg, Travis M.; Holland, Patrick L. & Cundari, Thomas R., 1964-
Description: Article discussing the cooperativity between low-valent iron and potassium promoters in dinitrogen fixation.
Contributing Partner: UNT College of Arts and Sciences
Carbon-Oxygen Bond Formation via Organometallic Baeyer-Villiger Transformations: A Computational Study on the Impact of Metal Identity

Carbon-Oxygen Bond Formation via Organometallic Baeyer-Villiger Transformations: A Computational Study on the Impact of Metal Identity

Date: December 20, 2011
Creator: Figg, Travis M.; Webb, Joanna R.; Cundari, Thomas R., 1964- & Gunnoe, T. Brent
Description: Article discussing a computational study on the impact of metal identity and carbon-oxygen bond formation via organometallic Baeyer-Villiger transformations.
Contributing Partner: UNT College of Arts and Sciences
Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron (III) Complex

Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron (III) Complex

Date: May 12, 2011
Creator: Cowley, Ryan E.; Eckert, Nathan A.; Vaddadi, Sridhar; Figg, Travis M.; Cundari, Thomas R., 1964- & Holland, Patrick L.
Description: This article discusses a mechanistic study of hydrogen atom transfer by an isolable iron (III) imido complex, LᴹᵉFeNAd (Lᴹᵉ = bulky β-diketiminate ligand, 2,4-bis(2,6-diisopropylphenylimido)pentyl; Ad = 1-adamantyl).
Contributing Partner: UNT College of Arts and Sciences
Flavin-Catalyzed Insertion of Oxygen into Rhenium-Methyl Bonds

Flavin-Catalyzed Insertion of Oxygen into Rhenium-Methyl Bonds

Date: July 24, 2010
Creator: Pouy, Mark J.; Milczek, Erika M.; Figg, Travis M.; Otten, Brooke M.; Prince, Bruce M.; Gunnoe, T. Brent et al.
Description: Article discussing flavin-catalyzed insertion of oxygen into rhenium-methyl bonds.
Contributing Partner: UNT College of Arts and Sciences