Synthesis of Ferrocene-based Ligands and Their Applications in Redox-switchable Catalysis for Selective Hydroamination Reactions
Author | : Brian Raymond Lydon |
Publisher | : |
Total Pages | : 67 |
Release | : 2013 |
ISBN-10 | : OCLC:868242684 |
ISBN-13 | : |
Rating | : 4/5 ( Downloads) |
Download or read book Synthesis of Ferrocene-based Ligands and Their Applications in Redox-switchable Catalysis for Selective Hydroamination Reactions written by Brian Raymond Lydon and published by . This book was released on 2013 with total page 67 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 [delta]-valerolactone monomers was calculated. Computational results correlated strongly with experimental data in that [delta]-valerolactones, which could not be polymerized, had a higher Gibbs free energy than cyclic carbonates, which could be polymerized.