Physical Sciences and Mathematics Commons^™

The Synthesis, Reactivity And Electrochemical Study Of Metallocene Substituted Α-Diimine Ligands, Eleanor Magdzinski

Electronic Thesis and Dissertation Repository

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 …

1,2,4-Triazine-Accelerated Azide-Alkyne Cycloaddition And Synthesis Of Metalloenzyme Inhibitors, Belinda Shea Lady

Doctoral Dissertations

The work of this dissertation describes the design and synthesis of 1,2,4-triazine ligands and other N-containing heterocycles and their use in the copper-catalyzed azide-alkyne cycloaddition (CuAAC). A variety of ligands were synthesized to probe the steric and electronic demands required for use in the CuAAC reaction. Substituents on the 1,2,4-triazine were systematically altered and the core 1,2,4-triazine modified to determine the most active ligand. Additional experiments explored the variability in the reaction conditions, such as solvent choice, use of reducing agents, and optimal stoichiometry. Under optimum conditions 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine and copper (II) tetrafluoroborate in the presence of triethylamine was found to …