This dissertation involves inorganic/organometallic catalysis models, in particular the functionalization of carbon-hydrogen and carbon-carbon bonds. Computational methods have been utilized to better understand the factors affecting the kinetics and thermodynamics of C−H and C−C bond activation/functionalization in this dissertation. Chapter 2 investigates methane C−H activation with a diiminopyridine nitride/nitridyl complex of 3d transition metals and main group elements via three competing pathways: 1,2-addition/[2 + 2] addition, insertion and H-atom abstraction/proton coupled electron transfer. Chapter 3 investigates a transition metal catalyzed C=C bond functionalization involving C−N bond formations to synthesize aziridines from aromatic and aliphatic alkenes. The study focuses on anionic 3d transition metal (M = Mn, Fe, Co and Ni) triphenylamide-amine complexes with nitrene active intermediates for the aziridination reactions. Chapter 4 investigates a disphenoidal Ni(II) azido complex participating in intramolecular C−H functionalization and amination via a putative Ni nitridyl intermediate and a 1,2-addition/[2 + 2] addition pathway. In Chapter 5, methane oxidative addition to the Cp*ML (Cp* = η5-C5Me5; M = Co, Rh, Ir , L = CO, PMe3) motif is compared and contrasted when the classic CO and PMe3 ligands are replaced with the cyclic alkyl(amino) carbene (CAAC) as ancillary ligands.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc1752352 |
| Date | 12 1900 |
| Creators | Sun, Zhicheng |
| Contributors | Cundari, Thomas, Slaughter, LeGrande M., Cisneros, Andres, Wang, Hong, Stavropoulos, Pericles |
| Publisher | University of North Texas |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | viii, 77 pages, Text |
| Rights | Public, Sun, Zhicheng, Copyright, Copyright is held by the author, unless otherwise noted. All rights Reserved. |
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