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

Abstract

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.

Authors:
; ;
Publication Date:
OSTI Identifier:
6612844
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 21:7
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Evans, W J, Wink, D J, and Stanley, D R. Reinvestigation of the reaction of tert-butyllithium with uranium tetrachloride: formation of catalytically active uranium(III) hydride complexes. United States: N. p., 1982. Web. doi:10.1021/ic00137a008.
Evans, W J, Wink, D J, & Stanley, D R. Reinvestigation of the reaction of tert-butyllithium with uranium tetrachloride: formation of catalytically active uranium(III) hydride complexes. United States. https://doi.org/10.1021/ic00137a008
Evans, W J, Wink, D J, and Stanley, D R. 1982. "Reinvestigation of the reaction of tert-butyllithium with uranium tetrachloride: formation of catalytically active uranium(III) hydride complexes". United States. https://doi.org/10.1021/ic00137a008.
@article{osti_6612844,
title = {Reinvestigation of the reaction of tert-butyllithium with uranium tetrachloride: formation of catalytically active uranium(III) hydride complexes},
author = {Evans, W J and Wink, D J and Stanley, D R},
abstractNote = {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.},
doi = {10.1021/ic00137a008},
url = {https://www.osti.gov/biblio/6612844}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 21:7,
place = {United States},
year = {Thu Jul 01 00:00:00 EDT 1982},
month = {Thu Jul 01 00:00:00 EDT 1982}
}