University of Illinois Urbana-Champaign

Investigating metallocofactor dynamics with biomimetic dinuclear cobalt complexes

Kelly, Kimberly A

Content Files
KELLY-THESIS-2021.pdf

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https://hdl.handle.net/2142/114025

Description

Title
Investigating metallocofactor dynamics with biomimetic dinuclear cobalt complexes
Author(s)
Kelly, Kimberly A
Issue Date
2021-12-09
Director of Research (if dissertation) or Advisor (if thesis)
Olshansky, Lisa
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
M.S.
Degree Level
Thesis
Date of Ingest
2022-04-29T21:47:47Z
Keyword(s)
  • intramolecular hydrogen-bond
  • cobalt-hydroxido
  • cobalt-hydroxo
  • bis(μ-oxo)
  • proton-coupled electron transfer
  • diamond core
  • bridging hydroxide
  • cobalt cubane
  • biomimetic metal complex
  • nonheme dinuclear active site.
Abstract
Hydrogen-bond (H-bond) networks play a critical role in nature, allowing enzymatic active sites to sequester substrates; control high-energy intermediates; and maintain structure, be it flexible or rigid. This work reports a series of dinuclear cobalt complexes: [Co2(μ–OH)2(μ-OAc)(κ1-OAc)2(pyR)4][PF6] (1R) where OAc = acetate and pyR = pyridine with para-substituent R. Complexes within the series span a range of electron-donating and withdrawing R groups, and are able to serve as structural models for a wide class of oxidase enzymes that feature an M2(µ-OH)2 diamond core. Critically, complexes within the series mimic scaffolds found in nature in that they are stabilized by H-bond interactions between μ–OH donors and κ1-OAc acceptors. The mechanism of reactivity is yet unknown, but the disruption of these networks via deprotonation has been studied in organic solvents, revealing a significant correlation between the electronics of the distal pyR upon the trans H-bonding network. The optimized conditions for the synthesis of the series are reported, and by affording the complex water-solubility via counterion exchange, the interconnected nature of solution pH and the resultant strength of the H-bonding network has also been explored. Efforts to extend the synthesis of the series into the heterobimetallic regime are not yet successful, but the presented results suggest that the μ–OH pKa can be tuned in the presence of intramolecular H-bond interactions to maintain stability and serve as a model for natural motifs.
Graduation Semester
2021-12
Type of Resource
Thesis
Permalink
http://hdl.handle.net/2142/114025
Copyright and License Information
Copyright 2021 Kimberly Kelly

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Graduate Dissertations and Theses at Illinois PRIMARY
Graduate Theses and Dissertations at Illinois