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Acid-mediated reactivity of organogold (III) complexes Yotam Ardon
- Format:
- Book
- Thesis/Dissertation
- Author/Creator:
- Ardon, Yotam, author.
- Language:
- English
- Subjects (All):
- Chemistry.
- Inorganic chemistry.
- Organic chemistry.
- 0485.
- 0488.
- 0490.
- Local Subjects:
- Chemistry.
- Inorganic chemistry.
- Organic chemistry.
- 0485.
- 0488.
- 0490.
- Genre:
- Academic theses
- Physical Description:
- 1 online resource (241 pages)
- Contained In:
- Dissertations Abstracts International 87-12B
- Place of Publication:
- Ann Arbor ProQuest Dissertations and Theses 2026
- Language Note:
- English
- Summary:
- The development of catalytic systems is crucial to ensure sustainable industrial-scale chemical production. This work describes mechanistic studies of homogeneous organogold(III) complexes relevant for aerobic oxidation catalysis. In Chapter 2, the hydrogenolysis of a AuIII-OH complex to form a AuIII-H is discussed. While reported for other late transition metal hydroxo species, this catalyst regeneration step is not known for Au. It was found that the hydrogenolysis of [(tBuPCP)AuIII-OH]OTf (tBuPCP = 2,6-C6H3(CH2PtBu2)2, OTf = triflate) to form [(tBuPCP)AuIII-H]OTf requires a Brønsted acid catalyst, a requirement not observed for the hydrogenolysis of other late metal hydroxos. A mechanistic investigation using kinetic studies and computational methods (density functional theory) reveals that hydrogenolysis proceeds through a solvent-assisted mechanism, and are consistent with the intermediacy of a novel AuIII-dihydrogen complex. Efforts to experimentally synthesize and characterize the AuIII-dihydrogen complex, described in Chapter 3, resulted in acid-catalyzed reductive elimination from the AuIII-H. The mechanism of reductive elimination was probed spectroscopically, revealing a surprising dependence on the identity of the acid catalyst that is not explained solely by acid strength. The mechanistic insights gained from Chapters 2-3 can unlock new pathways for aerobic oxidation catalyzed by AuIII in the presence of acid. Based on these results, as well as literature results suggesting that protic functionalities play a crucial role in metal-catalyzed olefin epoxidation reactions, a series of novel protic pincer ligands was synthesized. These efforts are described in Chapter 4
- Notes:
- Source: Dissertations Abstracts International, Volume: 87-12, Section: B.
- Advisors: Goldberg, Karen I. Committee members: Tomson, Neil C.; Kozlowski, Marisa C.; Mindiola, Daniel J.
- Ph.D. University of Pennsylvania 2026
- Vendor supplied data
- Local Notes:
- School code: 0175
- ISBN:
- 9798247979982
- Access Restriction:
- Restricted for use by site license
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