The Synthesis, Reactivity and Electrochemical Study of Metallocene Substituted α-Diimine Ligands

Author

Eleanor Magdzinski, The University of Western OntarioFollow

Degree

Master of Science

Program

Chemistry

Supervisor

Dr. Paul J. Ragogna

Abstract

The synthesis of transition metal complexes containing redox-active ligands or ligands with redox-active substituents have been areas of ongoing interest in chemical research. To date, only a handful of examples involving redox-active ligands containing main group centres have been reported.

This thesis presents work on the development of novel redox-active ligands utilizing an assortment of nitrogen-based frameworks (diiminopyridine (DIMPY), 1,4-diaza-1,3-butadiene (DAB), N-heterocyclic carbene (NHC)) that contain metallocene substituents (ferrocene and an understudied redox-active Co(III) moiety). Initially the syntheses of an N, N’-differocenyl diiminopyridine and its low-valent chalcogen (S²⁺, Se²⁺, Te²⁺) and pnictogen (P⁺) complexes are discussed. These complexes represent the first such examples of utilizing low-valent main group systems containing redox-active ligands with pendant ferrocenyl substituents. Other work focuses on the synthesis of the above listed nitrogen-based ligands containing novel mixed sandwich Co(III) substituents, and include comparative reactivity studies (SnCl₂ and GeCl₂.dioxane for DIMPY and SnCl₄ and Pt₂Me₄(SMe₂)₂ for DAB) of those ligands to their ferrocene derivatives. Electrochemical studies reveals an instability of the Co(III) containing complexes, leading to the continuous variation in the ligand framework towards a more stable compound.

Recommended Citation

Magdzinski, Eleanor, "The Synthesis, Reactivity and Electrochemical Study of Metallocene Substituted α-Diimine Ligands" (2013). Electronic Thesis and Dissertation Repository. 1615.
https://ir.lib.uwo.ca/etd/1615