Bidentate, tetradentate, and hexadentate ligands, with N₂, N₄, and S₂N₄ donor sets were complexed with Cu(II) and Ni(II) to form chiral and achiral chelates in an attempt to prepare complexes that allowed for the access of multiple oxidation states through electrochemical methods. The bidentate ligands were prepared from pyrrole-2-carboxaldehyde and chiral and achiral amines and anilines, and were complexed with the desired metal in a 2:1 ratio, with chiral ligands resulting in chiral complexes. Analogous ligands with N₄ coordination spheres were also prepared using pyrrole-2-carboxaldyhyde and various diamines, and were complexed in a 1:1 fashion. The tetradentate ligands were prepared using vinylpyridine and chiral piperazine derivatives to form both enantiomers of the chiral complexes, as well as similar non-chiral mono and dinuclear complexes using achiral derivatives of piperazine and homopiperazine. The hexadentate ligands were synthesized from 2-hydrazinopyridine and alkyl and aryl bridged dithio-diketo precursors, which were prepared using either a N,N,N-triethyl-N-(propan-2-onyl)ammonium or N,N,N-triethyl-N-(phenylethan-2-onyl)ammonium chloride salt and a range of dithiols. Synthetic, crystallographic, and absorption data will be presented as well as circular dichroism (CD) data for the chiral complexes and magnetic data for the dinuclear complex. Complexes were also characterized using electrochemistry and ESR.
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Title
Chiral and Achiral Copper(II) and Nickel(II) Complexes with Novel Multidentate Ligands
Creators
Molly A. O'Connor - DU
Contributors
Anthony William Addison (Advisor) - Drexel University (1970-)
Awarding Institution
Drexel University
Degree Awarded
Doctor of Philosophy (Ph.D.)
Publisher
Drexel University; Philadelphia, Pennsylvania
Resource Type
Dissertation
Language
English
Academic Unit
College of Arts and Sciences; Chemistry; Drexel University
Other Identifier
4312; 991014632534904721
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