Observations on the thermal decomposition of some uranium(IV) tetraalkyls

Tobin Jay Marks*, Afif M. Seyam

*Corresponding author for this work

Research output: Contribution to journalArticle

49 Citations (Scopus)

Abstract

The thermally unstable products of the reactions 4 RLi + UCl4 (R = various alkyl groups), presumed to be uranium tetraalkyls, decompose readily at room temperature in ethereal or hydrocarbon solvents. When R contains a β-hydrogen, comparable quantities of alkane (RH) and alkene (RH-H2) are produced along with trace amounts of the dimer, RR. This result indicates that uranium alkyl compounds readily decompose via β-hydrogen elimination under the appropriate circumstances (coordinative unsaturation). When a β-hydrogen is not present, the alkane, RH, is the major product. That stereochemistry is retained at the α-carbon atom of the 2-cis- and 2-trans-2-butenyl compounds suggests that 2-butenes are not formed from free R- radicals.

Original languageEnglish (US)
Pages (from-to)61-66
Number of pages6
JournalJournal of Organometallic Chemistry
Volume67
Issue number1
DOIs
StatePublished - Jan 1 1974

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Uranium
uranium
thermal decomposition
Hydrogen
Alkanes
Pyrolysis
Hot Temperature
Paraffins
alkanes
Uranium Compounds
hydrogen
Uranium compounds
alkyl compounds
Stereochemistry
stereochemistry
Alkenes
butenes
products
Hydrocarbons
Butenes

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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abstract = "The thermally unstable products of the reactions 4 RLi + UCl4 (R = various alkyl groups), presumed to be uranium tetraalkyls, decompose readily at room temperature in ethereal or hydrocarbon solvents. When R contains a β-hydrogen, comparable quantities of alkane (RH) and alkene (RH-H2) are produced along with trace amounts of the dimer, RR. This result indicates that uranium alkyl compounds readily decompose via β-hydrogen elimination under the appropriate circumstances (coordinative unsaturation). When a β-hydrogen is not present, the alkane, RH, is the major product. That stereochemistry is retained at the α-carbon atom of the 2-cis- and 2-trans-2-butenyl compounds suggests that 2-butenes are not formed from free R- radicals.",
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Observations on the thermal decomposition of some uranium(IV) tetraalkyls. / Marks, Tobin Jay; Seyam, Afif M.

In: Journal of Organometallic Chemistry, Vol. 67, No. 1, 01.01.1974, p. 61-66.

Research output: Contribution to journalArticle

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AB - The thermally unstable products of the reactions 4 RLi + UCl4 (R = various alkyl groups), presumed to be uranium tetraalkyls, decompose readily at room temperature in ethereal or hydrocarbon solvents. When R contains a β-hydrogen, comparable quantities of alkane (RH) and alkene (RH-H2) are produced along with trace amounts of the dimer, RR. This result indicates that uranium alkyl compounds readily decompose via β-hydrogen elimination under the appropriate circumstances (coordinative unsaturation). When a β-hydrogen is not present, the alkane, RH, is the major product. That stereochemistry is retained at the α-carbon atom of the 2-cis- and 2-trans-2-butenyl compounds suggests that 2-butenes are not formed from free R- radicals.

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