High-valent copper-dioxygen assemblies : synthesis, characterization, and potential relevance to biological systems

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Abstract/Contents

Abstract
Biological enzymes utilize various copper-based active sites to activate dioxygen creating a variety of copper-dioxygen assemblies. These assemblies carry out highly selective and difficult oxidative transformations vital to biological life. Insight into how Nature has optimized these active sites can be gleaned by studying synthetic structural mimics and has potential to be of great benefit to the industrial design of catalysts. While the resting structures of many of these active sites are known, the nature of the active oxidants are often less well-defined. In this thesis, efforts towards the cryogenic synthesis and spectroscopic characterization of copper(III)-containing oxidants, formed directly via dioxygen activation of biomimetic copper precursors, will be discussed. This work demonstrates both the kinetic and thermodynamic accessibility of the copper(III) oxidation state under biological ligation, which challenges existing assumptions in the literature through the identification of reactive intermediates.

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 2021; ©2021
Publication date 2021; 2021
Issuance monographic
Language English

Creators/Contributors

Author Keown, William Jay
Degree supervisor Stack, T. (T. Daniel P.), 1959-
Thesis advisor Stack, T. (T. Daniel P.), 1959-
Thesis advisor Cui, Yi, 1976-
Thesis advisor Solomon, Edward I
Degree committee member Cui, Yi, 1976-
Degree committee member Solomon, Edward I
Associated with Stanford University, Department of Chemistry

Subjects

Genre Theses
Genre Text

Bibliographic information

Statement of responsibility William Keown.
Note Submitted to the Department of Chemistry.
Thesis Thesis Ph.D. Stanford University 2021.
Location https://purl.stanford.edu/pw029qz2487

Access conditions

Copyright
© 2021 by William Jay Keown
License
This work is licensed under a Creative Commons Attribution 3.0 Unported license (CC BY).

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