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Authors: Stieber, Sabine Chantal Eileen
Advisors: Chirik, Paul J
DeBeer, Serena
Contributors: Chemistry Department
Keywords: redox-active
Subjects: Inorganic chemistry
Issue Date: 2013
Publisher: Princeton, NJ : Princeton University
Abstract: The electronic structures of bis(imino)pyridine iron compounds (<super>iPr</super>PDI)FeL; (<super>iPr</super>PDI =2,6-(2,6-<super>i</super>Pr2C6H3N=CMe)2C5H3N; L = ligand) were explored and are of relevance to a variety of fundamental transformations including oxidative addition, olefin coordination, processes relevant to nitrogen fixation and catalytic reactions including hydrogenation and polymerization of olefins. The known redox-activity of the bis(imino)pyridine ligand complicates the determination of the electronic structures of pre-catalysts and intermediates and raises questions regarding the electron flow in catalysis by these systems. This system allows for a series of unusual high spin (pseudo) square planar iron compounds to be isolated, which display single molecule magnet behavior. To understand both iron and ligand oxidation states, fundamental studies of contributions to iron and nitrogen K-edge X-ray absorption (XAS) and iron K&beta; X-ray emission (XES) spectroscopies have been undertaken. The results establish that iron and nitrogen K-edge XAS are sensitive to ligand oxidation state, but iron K&beta; XES is not. The overall results of synthetic, spectroscopic and computational studies suggest that the redox-active bis(imino)pyridine ligand allows for iron to maintain the preferred iron(II)-(III) redox couple and avoid high iron oxidation states.
Alternate format: The Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the library's main catalog
Type of Material: Academic dissertations (Ph.D.)
Language: en
Appears in Collections:Chemistry

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