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Chiral and achiral copper(II) and nickel(II) complexes with novel multidentate ligands
Dissertation   Open access

Chiral and achiral copper(II) and nickel(II) complexes with novel multidentate ligands

Molly A. O'Connor
Doctor of Philosophy (Ph.D.), Drexel University
Aug 2013
DOI:
https://doi.org/10.17918/etd-4312
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Abstract

Chemistry Chirality Ligands
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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