As of 2014, there is an expected 69,000 metric tons of nuclear waste sitting in storage in the U.S. Little efforts have been made to
deal with the radiotoxicity of the spent nuclear fuel (SNF). The problem arises from the complex mixture of the SNF and highly radioactive
actinides. Due to the high radioactivity of the minor actinides (Pu-Cm), there is a lack of understanding the fundamental chemistry of the
actinides. The focus of this work is to prepare coordination complexes that can be used as probes for elucidating changes in the structure
and bonding across the actinides series Most coordination chemistry that has been studied with the actinide series has only utilized ligands
stable to oxygen and moisture due to the difficulties of handling the transuranium actinides. The chemistry of non-aqueous ranium has made
great progress, while, the non-aqueous chemistry of the transuranic elements is relatively unexplored and offers a wider platform for
exploring methods of deducing electronic structure and information about the actinide-ligand bond. Such information can be very useful for
discovering trends in the whole series. The beginning chapters focus on simple coordination compounds using soft N and S donor ligands for
complexing Am-Cf. Since very little structure data is known for these elements and softer donor ligands have shown to have a preference over
trivalent actinides than lanthanides, we focus on these systems to understand the trends in bonding across the 5f series. Chapter 4 focus on
a series (U-Cf) of complexes using the redox active ligand 2,4,6,8-tetrakis(tert-butyl)-9-hydroxyphenoxanone (HDOPO) were synthesized in
non-aqueous conditions under an inert atmosphere and have been fully characterized by X-ray, optical, magnetic, and computational techniques.
Spectroscopic data reveals the An(DOPO)3 complexes of the earlier actinides being the tetravalent state, in contrast to the later actinides,
they are in the trivalent state. Furthermore, the Cf(III) complex disrupts the tris-chelate trend due to radiolysis. It is also shown that
the ligand undergoes redox transitions to stabilize the higher oxidation states of the earlier actinides. The results will help contribute
toward gaining foundational knowledge of structure and bonding in non-aqueous transuranic chemistry as well as give insight into the
participation of f-orbitals in bonding. The ending chapters are out of the scope of non-aqueous chemistry but projects that pertain to the
nature of the actinide series. As the first focuses on the effects of radiolysis. As we go to the heavier actinides, radiolysis affects the
crystallization of our targeted products. In this case, an aged thorium source produces peroxide over time changing the result of the
product. Lastly, is an example of driven degeneracy covalency in an americium chromate system. It was thought the later actinides tend to be
more ionic, however we are finding small amount of covalent character partakes in the bonding. Collectively, this body of work primary focus
is elucidating the structure and bonding of the f-elements through coordination complexes utilizing various techniques. / A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the
requirements for the degree of Doctor of Philosophy. / Fall Semester 2017. / November 13, 2017. / Includes bibliographical references. / Vladimir Dobrosavljević, University Representative; Kenneth Hanson, Committee Member; Michael Shatruk,
Committee Member.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_604967 |
| Contributors | Galley, Shane S. (author), Dobrosavljević, Vladimir (university representative), Hanson, Kenneth G. (committee member), Shatruk, Mykhailo (committee member), Florida State University (degree granting institution), College of Arts and Sciences (degree granting college), Department of Chemistry and Biochemistry (degree granting departmentdgg) |
| Publisher | Florida State University |
| Source Sets | Florida State University |
| Language | English, English |
| Detected Language | English |
| Type | Text, text, doctoral thesis |
| Format | 1 online resource (132 pages), computer, application/pdf |
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