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

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.

Name thesis:degree_name

M Sc

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

The University of Western Ontario

Year dc:date.issued

2013

Author dc:creator

• Magdzinski, Eleanor

Advisor dc:contributor.advisor

• Paul J. Ragogna

• Nitrogen based ligands
• redox-active ligands
• non-innocent ligands
• N-heterocyclic carbenes
• main group complexes
• diiminopyridine
• 1
• 4-diaza-1
• 3-butadiene

Language dc:language.iso

en_ca

Handle dc:identifier.uri

https://hdl.handle.net/20.500.14721/36577

OAI identifier oai:identifier

oai:uwo.scholaris.ca:20.500.14721/36577