Small changes big impact, ligand influence on dioxygen, semiquinone, and phenoxyl radical copper complexes
Abstract/Contents
- Abstract
- Reductive activation of dioxygen by copper to generate potent oxidants for multi- electron organic transformations is exploited extensively in biological systems. This thesis focuses on two types of multi-electron oxidants: Cu2O2 complexes and copper complexes with redox-active ligands. The goal of this work is to identify the influence of nitrogen containing ancillary ligands on properties of dioxygen, semiquinone and phenoxyl radical complexes of copper. This work is aimed primarily at synthetic chemists interested in rational design of ligands for creating bio-inspired oxidants and oxidation catalysts. Chapter 1 of this thesis reports the identification of a Density Functional Theory (DFT) protocol for deriving structure-property relationships in Cu2O2 complexes. Chapter 2 of this thesis applies towards modeling electronic spectra, the DFT protocols that were validated in Chapter 1 for modeling thermodynamics. Chapter 3 of this thesis describes the properties and reactivity of Cu2O2 complex generated from a new hybrid permethylated-amine-guanidine ligand based on a 1,3- propanediamine backbone (2L). Chapter 4 of this thesis describes the characterization of an intermediate (C) that is observed in both phenol hydroxylation and catechol oxidation with the SP core supported by N1, N2-di-t-butylethane-1,2-diamine (DBED). Chapter 5 of this thesis describes the influence of sulfanyl substituents on the optical and redox properties of copper-bonded phenoxyls.
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 | Verma, Prateek |
|---|---|
| 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 | Boxer, Steven G. (Steven George), 1947- |
| Thesis advisor | Solomon, Edward I |
| Advisor | Boxer, Steven G. (Steven George), 1947- |
| Advisor | Solomon, Edward I |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Pratik Verma. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Ph.D. Stanford University 2012 |
| Location | electronic resource |
Access conditions
- Copyright
- © 2012 by Prateek Verma
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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