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

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.

Name thesis:degree_name

M.S.

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2024

Author dc:creator

• Wahlmeier, Amy J

Contributors dc:contributor

• Mirica, Liviu M

• Organometallic Compounds
• High-valent Pd Species
• C-o Bond Formation
• Chemoselectivity
• Green Oxidants

Statement dc:rights

• Copyright 2024 Amy Wahlmeier

Language dc:language

en, eng

Handle dc:identifier

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

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F125767