Synthetic and mechanistic study of oxycarbene-like coupling reaction patterns of actinide eta/sup 2/-acyl complexes with carbon monoxide and isocyanides
Journal Article
·
· J. Am. Chem. Soc.; (United States)
This contribution reports the synthesis and characterization of the ylide complexes Cp'/sub 2/Th(OC(CH/sub 2/-t-Bu)C-(PR/sub 3/)O((Cl) (Cp' = eta/sup 5/-C/sub 5/Me/sub 5/; R = Me, Ph) formed by the carbonylation of Cp'/sub 2/Th(Cl)(eta/sup 2/-COCH/sub 2/-t-Bu) (1) in the presence of phosphines. Isotopic tracer studies with /sup 13/CO indicate that the labeled carbon atom is incorporated regiospecifically at the ylide ..cap alpha..-carbon atom position. The carbonylation of 1 to yield the enedionediolate (Cp'/sub 2/Th(OC(CH/sub 2/-t-Bu)CO)(Cl))/sub 2/ (2) or the ylide complexes was found to obey a second-order rate law where rate = kP/sub CO/(1); k = 1.50 (5) x 10/sup -5/ min/sup -1/ torr/sup -1/ for both carbonylations at 30.8 /sup 0/C. The rate of formation of the ylide complexes was also found to be independent of solvent, phosphine concentration, and type of phosphine used. The carbonylation of 1 is therefore inferred to involve a rate-determining coupling of CO with the acyl to yield an intermediate ketene or ketene-like complex. 51 references, 4 figures, 3 tables.
- Research Organization:
- Northwestern Univ., Evanston, IL
- OSTI ID:
- 5825624
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:1; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLATION
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CYANIDES
DATA
EXPERIMENTAL DATA
INFORMATION
KINETICS
LABELLED COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
SYNTHESIS
THORIUM COMPLEXES
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPLEXES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLATION
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
CYANIDES
DATA
EXPERIMENTAL DATA
INFORMATION
KINETICS
LABELLED COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
SYNTHESIS
THORIUM COMPLEXES