Synthesis, Characterization, and Reactivity Studies of Iron Complexes Supported by the Redox-Active [ONO] Ligand
- Author(s): Wong, Janice Lin
- Advisor(s): Heyduk, Alan F.
- et al.
The work reported herein primarily focuses on the development of new platforms for multi-electron reactivity using iron complexes supported by a redox-active pincer-type ligand. This dissertation details the synthesis, characterization, and reactivity of iron complexes coordinated to the redox-active [ONO] ([ONO]H3 = bis(3,5-di-tert-butyl-2-phenol)amine) ligand.
Chapter 1 provides a general background on ligand-centered and metal-centered redox reactivity. Specifically, the characteristics of redox-active ligands and their ability to promote multi-electron reactivity at redox-inert metal centers is presented. In addition, iron-catalyzed organic transformations in which the metal center undergoes redox changes is also discussed. Finally, ligand-enabled redox reactions mediated by iron complexes containing redox-active ligands is described.
Chapter 2 reports on the complexation of bis(3,5-di-tert-butyl-2-phenoxy)amine, [ONHO], and the redox-active [ONO] ligands by iron centers to afford a new family of iron complexes. Characterizations of each compound through a battery of analytical techniques reveal the oxidation states of the metal center and ligand. Furthermore, the electronic properties of each complex were investigated in order to evaluate their potential to facilitate multi-electron reactivity.
Chapter 3 details the reactivity of the [ONO]Fe platform. Metathesis reactions are conducted with [ONOq]FeIIIX2 (X = Cl, N[SiMe3]2) complexes, demonstrating the capability of the fully-oxidized [ONOq]1&ndash to act as a two-electron acceptor to generate the fully reduced [ONOcat]3&ndash that is coordinated to an iron(III) center. Similarly, oxidation of [ONOcat]FeIII(py)3 (py = pyridine) using dihalogens result in two-electron oxidations of the tridentate ligand while the metal oxidation state remains the same. These redox reactions showcase the ability of the [ONO] ligand platform to undergo reversible two-electron oxidation state changes, allowing multi-electron reactivity to occur at the iron center.
The synthesis and characterization of two novel bimetallic complexes of the form [ONO]M'[ONO]2M (M' = Fe, Zn; M = Fe) are presented in Chapter 4. The rich redox profiles of both complexes suggest that they can potentially impart unique cooperative bimetallic reactivity. The synthetic techniques developed to prepare these complexes lay the foundation for a general method to access new bimetallic combinations that could be promising for multi-electron reactivity.
Finally, Chapter 5 discusses the synthesis, characterization, and electronic comparisons between two homoleptic tris-iminosemiquinonate chromium(III) compounds. While one is coordinated to three N,N'-bis(3,5-dimethylphenyl)acenapthenediimino-semiquinonate, (dmp-ADIsq)1&ndash, ligands, the other contains three N,N'-bis(3,5-dimethylphenyl)phenanthrenediimino-semiquinonate, (dmp-PDIsq)1&ndash, ligands. The differences in the electronic properties between each complex likely stems from variation in the diimine ligand backbones. However, further investigation is required to completely understand the complicated behaviors of such complexes, both of which apparently exhibit intramolecular anti-ferromagnetic properties.