Computational Study of Small Molecule Activation via Low-Coordinate Late First-Row Transition Metal Complexes

Computational Study of Small Molecule Activation via Low-Coordinate Late First-Row Transition Metal Complexes

Date: May 2010
Creator: Pierpont, Aaron
Description: Methane and dinitrogen are abundant precursors to numerous valuable chemicals such as methanol and ammonia, respectively. However, given the robustness of these substrates, catalytically circumventing the high temperatures and pressures required for such transformations has been a challenging task for chemists. In this work, computational studies of various transition metal catalysts for methane C-H activation and N2 activation have been carried out. For methane C-H activation, catalysts of the form LnM=E are studied, where Ln is the supporting ligand (dihydrophosphinoethane or β-diketiminate), E the activating ligand (O, NCH3, NCF3) at which C-H activation takes place, and M the late transition metal (Fe,Co,Ni,Cu). A hydrogen atom abstraction (HAA) / radical rebound (RR) mechanism is assumed for methane functionalization (CH4 à CH3EH). Since the best energetics are found for (β-diket)Ni=O and (β-diket)Cu=O catalysts, with or without CF3 substituents around the supporting ligand periphery, complete methane-to-methanol cycles were studied for such systems, for which N2O was used as oxygen atom transfer (OAT) reagent. Both monometallic and bimetallic OAT pathways are addressed. Monometallic Fe-N2 complexes of various supporting ligands (LnFe-N2) are studied at the beginning of the N2 activation chapter, where the effect of ligand on N2 activation in end-on vs. side-on N2 isomers ...
Contributing Partner: UNT Libraries
Catalytic Tuning of a Phosphinoethane Ligand for Enhanced C-H Activation

Catalytic Tuning of a Phosphinoethane Ligand for Enhanced C-H Activation

Date: September 5, 2008
Creator: Cundari, Thomas R., 1964-; Jimenez-Halla, J. Oscar C.; Morello, Glenn R. & Vaddadi, Sridhar
Description: This article discusses catalytic tuning of a phosphinoethane ligand for enhanced C-H activation.
Contributing Partner: UNT College of Arts and Sciences
Comparative Reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): Impact of Ancillary Ligand L on Activation of Carbon-Hydrogen Bonds Including Catalytic Hydroarylation and Hydrovinylation/Oligomerization of Ethylene

Comparative Reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): Impact of Ancillary Ligand L on Activation of Carbon-Hydrogen Bonds Including Catalytic Hydroarylation and Hydrovinylation/Oligomerization of Ethylene

Date: May 9, 2007
Creator: Foley, Nicholas A.; Lail, Marty; Lee, John P.; Gunnoe, T. Brent; Cundari, Thomas R., 1964- & Petersen, Jeffrey L.
Description: This article discusses comparative reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3).
Contributing Partner: UNT College of Arts and Sciences
Ptᴵᴵ-Catalyzed Ethylene Hydrophenylation: Influence of Dipyridyl Chelate RIng Size on Catalyst Activity and Longevity

Ptᴵᴵ-Catalyzed Ethylene Hydrophenylation: Influence of Dipyridyl Chelate RIng Size on Catalyst Activity and Longevity

Date: May 3, 2013
Creator: McKeown, Bradley A.; Gonzalez, Hector Emanuel; Gunnoe, T. Brent; Cundari, Thomas R., 1964- & Sabat, Michal
Description: Article discussing Ptᴵᴵ-catalyzed ethylene hydrophenylation.
Contributing Partner: UNT College of Arts and Sciences