Syntheses and characterization of (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/U(NR/sub 2/)/sub 2/ compounds
- Lawrence Berkeley Lab., CA
The reaction of 2 equivalents of cyclopentadiene with U(NPr/sub 2/)/sub 4/ and U(NPh/sub 2/)/sub 4/ and the reaction of 1.5 equivalents of cyclopentadiene with U(NEt/sub 2/)/sub 4/, generated in situ, gives the corresponding Cp/sub 2/U(NR/sub 2/)/sub 2/ complexes in good yields. However, U(N-i-Pr/sub 2/)/sub 4/ does not react with cyclopentadiene at room temperature and U(NMe/sub 2/)/sub 4/ gives mixture of Cp/sub 2/U(NMe/sub 2/)/sub 2/ and Cp/sub 3/U(NMe/sub 2/). Excess cyclopentadiene also reacts with Cp/sub 2/U(NEt/sub 2/)/sub 2/ to produce Cp/sub 3/U(NEt/sub 2/). The transamination reaction of Cp/sub 2/U(NEt/sub 2/)/sub 2/ with pyrrole and 2,3-dimethylpyrrole gives mixtures of products only; however, ethyl 3,4,5-trimethylpyrrole-2-carboxylate gives Cp/sub 2/U(NC/sub 4/Me/sub 3/(COOEt))/sub 2/, and the reaction with 1 equivalent of diphenylamine yields Cp/sub 2/U(NEt/sub 2/)(NPh/sub 2/). It is argued that the reactivity sequence and the stability of Cp/sub 2/U(NR/sub 2/)/sub 2/ compounds are best explained by steric effect considerations. The spectral characteristics of the Cp/sub 2/U(NR/sub 2/)/sub 2/ complexes are presented which show that the compounds possess eta/sup 5/-cyclopentadienyl moieties and monomeric solution behavior with no primary solvent interaction. In Cp/sub 2/U(NC/sub 4/Me/sub 3/(COOEt))/sub 2/, additional interaction between uranium and oxygen of the carboxylate functionality is postulated.
- DOE Contract Number:
- W-7405-ENG-48
- OSTI ID:
- 6231578
- Journal Information:
- Inorg. Chem.; (United States), Vol. 20:8
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
CARBOXYLIC ACID ESTERS
CHEMICAL REACTIONS
PYRROLES
URANIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
AMIDES
CYCLOPENTADIENE
EXPERIMENTAL DATA
LIGANDS
NMR SPECTRA
SPECTROSCOPY
STABILITY
ACTINIDE COMPLEXES
ALKENES
AZOLES
COMPLEXES
CYCLOALKENES
DATA
DIENES
ESTERS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
POLYENES
SPECTRA
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials