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Author Arduini, A. L. ♦ Edelstein, N. M. ♦ Reynolds, J. G. ♦ Schmid, K. ♦ Takats, J.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY ♦ 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 ♦ Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials
Abstract 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.
Educational Use Research
Learning Resource Type Article
Publisher Date 1981-08-01
Publisher Place United States
Journal Inorg. Chem.
Volume Number 20
Issue Number 8


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