The investigation of carbon-fluorine bond activation by uranium and evaluation of a tris-oxazoline based tripodal ligand to support low-valent uranium centers
Abstract
The collective knowledge regarding the behavior of actinides, and in particular, uranium is still very low when compared to that of most transition metals. This is interesting and potentially problematic given the importance of actinides in the nuclear fuel cycle. To further our understanding of uranium we have explored the stability and reactivity of uranium complexes bearing tris(4,4’-dimethyl-2H-oxazolinyl)phenylborate ligands (To M). To date, we have found that the ToM ligand supports uranium centers in the three and four oxidation states quite well. Additionally, an improved large scale synthesis of chiral oxazolines is presented, along with attempts at metalation with uranium centers through salt metathesis and protonolysis reactions. The ability of the complex Tp*2UCH2Ph to activate carbon-fluorine bonds of various substrates has been investigated. Compared to prior results for uranium(IV) complexes, our results can be viewed as having greater synthetic utility. Additionally, two new terminal uranium-fluoride structures were discovered as part of this work. This is significant due to the limited structural information available concerning U-F bonds, coupled with the importance of UF6 in nuclear fuel processing.
Degree
Ph.D.
Advisors
Bart, Purdue University.
Subject Area
Inorganic chemistry
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