Reinvestigation of the reaction of tert-butyllithium with uranium tetrachloride: formation of catalytically active uranium(III) hydride complexes

Journal Article · Thu Jul 01 00:00:00 EDT 1982 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00137a008· OSTI ID:6612844

Evans, W J; Wink, D J; Stanley, D R

The reaction of UCl/sub 4/ with t-C/sub 4/H/sub 9/Li in alkane solvents has been reinvestigated in detail by quantitative collection and identification of gaseous products and by spectral, analytical, and chemical characterization of the solid uranium products. Treatment of UCl/sub 4/ with 4 equiv of t-C/sub 4/H/sub 9/Li generates 1.5 to 1.8 equiv of 2-methylpropane and 2-methylpropene in a 2.5-3 to 1 ratio and a solid U(III) hydride product which readily dissolves in tetrahydrofuran (THF). As much as 1.7 equiv of the starting alkyllithium reagent can be recovered unreacted in this reaction, and hence the primary features of the reaction can be reproduced by using only 2 equiv of t-C/sub 4/H/sub 9/Li. Reaction of 1 equiv of t-C/sub 4/H/sub 9/Li with UCl/sub 4/ forms a U(III) product free of hydride. The reaction of n-C/sub 4/H/sub 9/Li with UCl/sub 4/ is similar. Detailed analysis of alkane/alkene ratios of gaseous products suggests that these systems abstract hydrogen from the alkane solvent possibly through a low-valent uranium center. The U(III) hydride product of these reactions is catalytically active in alkyne and alkane hydrogenation reactions conducted under mild conditions.

• OSTI ID: 6612844
• Journal Information: Inorg. Chem.; (United States), Vol. 21:7
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
2-METHYLPROPANE
CHEMICAL REACTION YIELD
2-METHYLPROPENE
LITHIUM COMPLEXES
CHEMICAL REACTIONS
URANIUM HYDRIDES
URANIUM TETRAFLUORIDE
ABSORPTION SPECTRA
ALKANES
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
GAS CHROMATOGRAPHY
GASES
INFRARED SPECTRA
LOW TEMPERATURE
MEDIUM TEMPERATURE
OPTICAL SPECTROMETERS
ORGANIC SOLVENTS
ORGANOMETALLIC COMPOUNDS
QUANTITATIVE CHEMICAL ANALYSIS
QUANTITY RATIO
SOLIDS
SOLUBILITY
TEMPERATURE DEPENDENCE
TETRAHYDROFURAN
TIME DEPENDENCE
ACTINIDE COMPOUNDS
ALKENES
CHEMICAL ANALYSIS
CHROMATOGRAPHY
COMPLEXES
DATA
FLUIDS
FLUORIDES
FLUORINE COMPOUNDS
FURANS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
REACTION KINETICS
SEPARATION PROCESSES
SOLVENTS
SPECTRA
SPECTROMETERS
URANIUM COMPOUNDS
URANIUM FLUORIDES
YIELDS
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials