Mechanical control of metal-ligand complexation and catalysis through surface immobilization
Abstract/Contents
- Abstract
- Heterogenization, or the covalent immobilization of discrete molecular species to a material surface, is a promising strategy in catalyst design to leverage high selectivity and ligand variability with the practical heterogeneous advantages of catalyst separation and recycling. Moreover, heterogenization can be used as a mechanical means to control intermolecular interactions and thereby probe reaction mechanisms in a way not achievable through purely homogeneous characterization. An ideal immobilization approach needs to be modular, with high degree of control over the total surface loading of a species and its overall surface distribution. Here we report the preparation and application of functionalized mesoporous silica SBA-15 with a silioxypropylazide incorporated through a co-condensation approach. These materials serve as the platform for the heterogenization of ethynylated organic moieties through the copper-catalyzed azide alkyne cycloaddition. Surface loading is controlled by the amount of azide incorporation during co-condensation, and the surface distribution of immobilized species correlates well with a statistically random model. Immobilized manganese complexes demonstrate rapid catalytic epoxidation and C−H hydroxylation with peracetic acid as the terminal oxidant. Through a controlled variation of the surface loading and a quantitative understanding of site-interactions, we examine the impact of multi-ligand binding and site-isolation on catalysis.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2012 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Smith, Brian Jacob |
|---|---|
| Associated with | Stanford University, Department of Chemistry |
| Primary advisor | Stack, T. (T. Daniel P.), 1959- |
| Thesis advisor | Stack, T. (T. Daniel P.), 1959- |
| Thesis advisor | Chidsey, Christopher E. D. (Christopher Elisha Dunn) |
| Thesis advisor | Fayer, Michael D |
| Advisor | Chidsey, Christopher E. D. (Christopher Elisha Dunn) |
| Advisor | Fayer, Michael D |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Brian J. Smith. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis (Ph.D.)--Stanford University, 2012. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2012 by Brian Jacob Smith
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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