Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms
Compounds (RC[sub 5]H[sub 4])[sub 3]U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC[sub 5]H[sub 4])[sub 3]UCl with t-BuLi (R = t-Bu, Me[sub 3]Si). Reactions of (MeC[sub 5]H[sub 4])[sub 3]U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC[sub 5]H[sub 4])[sub 3]ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC[sub 5]H[sub 4])[sub 4]U compounds is next considered. Reaction of the trivalent (RC[sub 5]H[sub 4])[sub 3]U with (RC[sub 5]H[sub 4])[sub 2]Hg results in formation of (RC[sub 5]H[sub 4])[sub 4]U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)
- Research Organization:
- Lawrence Berkeley Lab., CA (United States)
- Sponsoring Organization:
- DOE; USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6566863
- Report Number(s):
- LBL-34031; ON: DE93015036
- Country of Publication:
- United States
- Language:
- English
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38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
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ACTINIDE COMPLEXES
ALKENES
AROMATICS
BASES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKENES
CYCLOPENTADIENE
DECOMPOSITION
DIENES
ELECTRON TRANSFER
HYDROCARBONS
KINETICS
LEWIS BASES
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SOLVENTS
ORGANOMETALLIC COMPOUNDS
POLYENES
REACTION KINETICS
RESONANCE
SOLVENTS
STEREOCHEMISTRY
SYNTHESIS
THORIUM COMPLEXES
URANIUM COMPLEXES