Master of Science
Dr. Paul J. Ragogna
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.
Magdzinski, Eleanor, "The Synthesis, Reactivity and Electrochemical Study of Metallocene Substituted α-Diimine Ligands" (2013). Electronic Thesis and Dissertation Repository. 1615.