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Synthesis of Ferrocene-Based Ligands and Their Applications in Redox-Switchable Catalysis for Selective Hydroamination Reactions

  • Author(s): Lydon, Brian Raymond
  • Advisor(s): Diaconescu, Paula L
  • et al.
Abstract

This thesis contains results from three different projects. The first project focused on the synthesis of monoanionic ferrocene-based N,P ligands. 1-(tert-butyldimethylsilyl)amino-1'-diphenylphosphinoferrocene (fc(TBSNH)(PPh2)) was successfully synthesized and characterized by 1H, 31P, 13C NMR spectroscopy, and elemental analysis. Unfortunately, coordination to group 3 metal complexes was unsuccessful.

The second project focused on the synthesis of redox-active ferrocene-based ligands and their applications in selective intramolecular hydroamination. Redox-active ligands can be used as a reversible trigger to control catalytic reactivity. Preliminary results observed by 1H NMR spectroscopy suggest that [1,1'-ferrocenedi(thio(3,5-di-tert-butyl-2-phenoxide)]Zr dibenzyl ((thiolfan2)ZrBn2) shows selectivity between primary and secondary alkeneamines depending on the oxidation state of the iron center.

The final project was a computational study using density functional theory (DFT) to understand recent experimental findings involving ferrocene-functionalized biodegradable polymers. Gibbs free energy for six cyclic carbonate monomers and three δ-valerolactone monomers was calculated. Computational results correlated strongly with experimental data in that δ-valerolactones, which could not be polymerized, had a higher Gibbs free energy than cyclic carbonates, which could be polymerized.

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