Nonclassical activation of carbon monoxide by organoactinides
- Northwestern Univ., Evanston, Il
This article reviews recent results on the carbonylation chemistry of bis(pentamethylcyclopentadienyl) thorium and uranium hydrocarbyl and dialkylamide complexes. Facile migratory insertion of carbon monoxide into metal-carbon and metal-nitrogen bonds is observed. In several cases bihaptoacyl and bihaptocarbamoyl complexes were isolated and characterized by single crystal x-ray diffraction. The great strength of the metal-oxygen bonding in these species is evident in metrical and spectral data, as well as in the reaction chemistry, which is decidedly alkoxycarbene-like. In the case of the bis(pentamethylcyclopentadienyl) actinide dialkyls, the final carbonylation products are C-C coupled cis-1,2-enediolate complexes, while for the corresponding bis(dialkylamides), the products are bis(carbamoyl) species. Both types of compound have been characterized by x-ray diffraction. The carbon monoxide chemistry observed here may be of relevance to mechanistic discussions of catalytic CO reduction, especially that involving actinide oxide or actinide oxide supported catalysts.
- OSTI ID:
- 6417498
- Report Number(s):
- CONF-790917-P4; TRN: 81-010642
- Journal Information:
- ACS Symp. Ser.; (United States), Vol. 131; Conference: American Chemical Society national meeting, Washington, DC, USA, 10 Sep 1979
- Country of Publication:
- United States
- Language:
- English
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Carbon monoxide activation by organoactinides: a comparative synthetic, thermodynamic, kinetic, and mechanistic investigation of migratory CO insertion into actinide-carbon and actinide-hydrogen bonds to yield eta/sup 2/-acyls and eta/sup 2/-formyls
Related Subjects
CARBONYLATION
THORIUM COMPLEXES
URANIUM COMPLEXES
CARBON MONOXIDE
REDUCTION
X-RAY DIFFRACTION
ACTINIDE COMPLEXES
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
OXIDES
OXYGEN COMPOUNDS
SCATTERING
400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials