Trivalent metallocene chemistry of some uranium, titanium, and zirconium complexes

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Dicyclopentadienyluranium halide dimers have been prepared and their solution behavior examined. These molecules exist as dimers in solution, and the halide ligands undergo rapid site exchange on the NMR timescale above 50 C. Analogous dicyclopentadienyluranium hydroxide dimers have also been prepared; they oxidatively eliminate hydrogen to give the corresponding oxide dimers. Mechanism of this reaction is consistent with {alpha}migration of one of the hydroxide hydrogen atoms to a uranium center followed by elimination of hydrogen. Ground state of [(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}]{sub 3}M M = Nd, U and their base adducts has been examined by variable temperature magnetic susceptibility ... continued below

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307 p.

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Lukens, W. W., Jr. May 1, 1995.

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Dicyclopentadienyluranium halide dimers have been prepared and their solution behavior examined. These molecules exist as dimers in solution, and the halide ligands undergo rapid site exchange on the NMR timescale above 50 C. Analogous dicyclopentadienyluranium hydroxide dimers have also been prepared; they oxidatively eliminate hydrogen to give the corresponding oxide dimers. Mechanism of this reaction is consistent with {alpha}migration of one of the hydroxide hydrogen atoms to a uranium center followed by elimination of hydrogen. Ground state of [(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}]{sub 3}M M = Nd, U and their base adducts has been examined by variable temperature magnetic susceptibility and EPR spectroscopy. The ground state is found to be {sup 4}I{sub 9/2} with a crystal field state consisting largely of J{sub z} = 1/2 lowest, in agreement with previous studies on tris-cyclopentadienylneodymium complexes. The zirconium metallocene Cp{sub 3}Zr has been prepared, characterized crystallographically, and its reactivity studied. Its chemical behavior is controlled by presence of an electron in the non-bonding, d{sub z}2 orbital which prevents formation of base adducts Of Cp{sub 3}Zr, but allows Cp{sub 3}Zr to abstract atoms from other molecules. Electonic and EPR spectra of Cp*{sub 2}TiX complexes, where Cp* is Me{sub 5}C{sub 5} and X is a monodentate, anionic ligand such as halide, have been studied. A {pi}-bonding spectrochemical series is developed, and trends in {pi}-bonding ability are found similar to those in other inorganic complexes. The {beta}-agostic interactions in Cp*{sub 2}TiN(Me)Ph have been examined using variable temperature EPR spectroscopy, and the enthalpy/entropy of the interaction determined. In Cp*{sub 2}TiEt, enthalpy of the {beta}-agostic interaction is {minus}1.9 kcal/mol. The titanocene anion, Cp*{sub 2}TiLi(TMEDA) (TMEDA is N,N,N`,N`-tetramethylethylenediamine), has been prepared and its structure determined.

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307 p.

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INIS; OSTI as DE96001061

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  • Other Information: TH: Thesis (Ph.D.)

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  • Other: DE96001061
  • Report No.: LBL--37646
  • Grant Number: AC03-76SF00098
  • Office of Scientific & Technical Information Report Number: 111895
  • Archival Resource Key: ark:/67531/metadc621122

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Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

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  • May 1, 1995

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  • June 16, 2015, 7:43 a.m.

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  • Aug. 23, 2016, 3:48 p.m.

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Lukens, W. W., Jr. Trivalent metallocene chemistry of some uranium, titanium, and zirconium complexes, thesis or dissertation, May 1, 1995; California. (digital.library.unt.edu/ark:/67531/metadc621122/: accessed June 22, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.