Synthesis, evaluation, and mechanistic analysis of ruthenium(II) precatalysts for C-H hydroxylation
Abstract/Contents
- Abstract
- Current efforts to improve C--H oxidation methodologies are constrained by the limited set of structurally flexible metal-ligand complexes capable of effecting such transformations. We describe the development of a synthetic route towards novel heteroleptic Ru(II) complexes bound to both a 2,2'-bipyridine ligand and a strong σ-donating bidentate group. The selective and convenient synthesis of these complexes is possible under mild conditions that promote Ru- cymene ligand substitution. Evaluation of these heteroleptic complexes as precatalysts for C--H oxidation resulted in the discovery of an efficient precatalyst that displays excellent stability and turnover numbers. In efforts to further develop this technology, mechanistic studies to identify catalyst speciation and decomposition pathways were undertaken. A combination of reaction kinetics analysis, isotopic labeling, mass spectrometry, and electrochemical measurements have revealed that ligand oxidation is critical for generating an active catalyst, and highlight reactivity and stability differences between homo- and heteroleptic Ru complexes. Insights gained from these studies should inform development of next-generation C--H oxidation catalysts.
Description
| Type of resource | text |
|---|---|
| Form | electronic resource; remote; computer; online resource |
| Extent | 1 online resource. |
| Place | California |
| Place | [Stanford, California] |
| Publisher | [Stanford University] |
| Copyright date | 2023; ©2023 |
| Publication date | 2023; 2023 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Lauridsen, Paul Joseph |
|---|---|
| Degree supervisor | Du Bois, Justin |
| Thesis advisor | Du Bois, Justin |
| Thesis advisor | Burns, Noah |
| Thesis advisor | Stack, T. (T. Daniel P.), 1959- |
| Degree committee member | Burns, Noah |
| Degree committee member | Stack, T. (T. Daniel P.), 1959- |
| Associated with | Stanford University, School of Humanities and Sciences |
| Associated with | Stanford University, Department of Chemistry |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Paul Joseph Lauridsen. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis Ph.D. Stanford University 2023. |
| Location | https://purl.stanford.edu/hn492nw4556 |
Access conditions
- Copyright
- © 2023 by Paul Joseph Lauridsen
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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