Please use this identifier to cite or link to this item: http://arks.princeton.edu/ark:/88435/dsp01nc580m73j
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dc.contributor.authorStieber, Sabine Chantal Eileenen_US
dc.contributor.otherChemistry Departmenten_US
dc.date.accessioned2013-05-21T13:33:52Z-
dc.date.available2013-05-21T13:33:52Z-
dc.date.issued2013en_US
dc.identifier.urihttp://arks.princeton.edu/ark:/88435/dsp01nc580m73j-
dc.description.abstractThe 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.en_US
dc.language.isoenen_US
dc.publisherPrinceton, NJ : Princeton Universityen_US
dc.relation.isformatofThe Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the <a href=http://catalog.princeton.edu> library's main catalog </a>en_US
dc.subjectredox-activeen_US
dc.subjectspectroscopyen_US
dc.subject.classificationInorganic chemistryen_US
dc.titleMETHODS FOR DETERMINING ELECTRONIC STRUCTURES AND MECHANISMS OF BIS(IMINO)PYRIDINE IRON PRE-CATALYSTSen_US