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Investigation of Metal-Ligand Cooperativity on the Reactivity of Metal Complexes Ryan P Murphy
- Format:
- Book
- Thesis/Dissertation
- Author/Creator:
- Murphy, Ryan P., author.
- Language:
- English
- Subjects (All):
- Chemistry.
- Biochemistry.
- Organic chemistry.
- Molecular chemistry.
- 0485.
- 0431.
- 0487.
- 0490.
- Local Subjects:
- Chemistry.
- Biochemistry.
- Organic chemistry.
- Molecular chemistry.
- 0485.
- 0431.
- 0487.
- 0490.
- Physical Description:
- 1 electronic resource (491 pages)
- Contained In:
- Dissertations Abstracts International 86-07B
- Place of Publication:
- Ann Arbor : ProQuest Dissertations and Theses, 2024
- Language Note:
- English
- Summary:
- Metal-ligand cooperativity offers new avenues of activating strong bonds under mild conditions. Herein, we describe three thrusts investigating the cooperativity of different metal and ligand systems. First, a series of Ni complexes ligated by a bis(phosphinimine) pincer ligand scaffold will be described. Their ability to undergo oxidation into the corresponding aminyl complexes are probed through EPR, UV-Vis spectroscopy, and Evans' Method. DFT calculations of these complexes further support the assignment of the generation of aminyl radical species, and the effect of ligand modification on the aminyl complexes will be explored. Second, a computational investigation into the aerobic dehydrogenation of indoline by a copper complex ligated with a tren-based tris(phosphinimine) ligand (tren = tris(2-aminoethyl)amine) will be described. Through the investigation of different complexation and activation routes, the utility of a flexible ligand scaffold with built-in bases will be highlighted. The coordination of indoline enables the complex to undergo a series of proton-coupled electron transfer (PCET) reactions, whereby indoline coordination facilitates the reduction of the copper center, making a viable activation pathway feasible at room temperature. Lastly, a computational investigation into σ-bond metathesis by a diiron macrocyclic complex will be discussed. The mechanism for the activation of C(sp)−C(sp2) bonds of alkynes is elucidated, and the reversibility of the activation is probed. Additional work exploring Lewis acid-mediated σ-bond metathesis with these activation complexes will be described
- Notes:
- Source: Dissertations Abstracts International, Volume: 86-07, Section: B.
- Advisors: Tomson, Neil C. Committee members: Mallouk, Thomas E.; Walsh, Patrick J.; Kozlowski, Marisa C.
- Ph.D. University of Pennsylvania 2024
- Local Notes:
- School code: 0175
- ISBN:
- 9798302184290
- Access Restriction:
- Restricted for use by site license
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