University of Illinois Urbana-Champaign

Oxidative reactivity of high-valent palladium complexes supported by 1,4,7-triisopropyl-1,4,7-triazacyclononane

Wahlmeier, Amy J

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https://hdl.handle.net/2142/125767

Description

Title
Oxidative reactivity of high-valent palladium complexes supported by 1,4,7-triisopropyl-1,4,7-triazacyclononane
Author(s)
Wahlmeier, Amy J
Issue Date
2024-07-01
Director of Research (if dissertation) or Advisor (if thesis)
Mirica, Liviu M
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
M.S.
Degree Level
Thesis
Keyword(s)
  • Organometallic compounds
  • High-valent Pd species
  • C-O Bond formation
  • Chemoselectivity
  • Green oxidants
Abstract
Reactivity through high-valent palladium intermediates has become a relevant tool in the pursuit of selective new bond formation under green catalytic reaction conditions. Due to its ability to provide new reaction opportunities, in-depth investigations of palladium complexes that can form high-valent intermediates are needed to effectively design and improve current catalytic palladium reactivity systems. Using the flexible tridentate ligand 1,4,7-triisopropyl-1,4,7-triazacyclononane (iPr3tacn), a variety of inorganic and organometallic palladium(II) complexes were synthesized in order to probe for new bond formation reactivity. Screening for fundamental oxidative reactions resulted in the new synthesized complex, (iPr3tacn)PdII(cycloneophyl) [cycloneophyl = -CH2CMe2-o-C6H4-], which produces promising chemoselective reactivity for both C–O and C–O–C bond formation through high-valent palladium intermediates. Additional mechanistic studies with intermediate characterizations for these C–O bond reactions were obtained to provide insight on the oxidant and ligand interactions occurring in solution to form the Pd(IV) intermediates. Finally, preliminary screening of a new complex undergoing C–H activation with C–O bond oxidation reactivity is discussed along with new proposed ligand and complex synthesis to generate future directions for high-valent palladium studies.
Graduation Semester
2024-08
Type of Resource
Thesis
Handle URL
https://hdl.handle.net/2142/125767
Copyright and License Information
Copyright 2024 Amy Wahlmeier

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