Double carbonylation of actinide bis(cyclopentadienyl) complexes. Experimental and theoretical aspects

Kazuyuki Tatsumi, Akira Nakamura, Peter Hofmann, Roald Hoffmann, Kenneth G. Moloy, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

This contribution presents a theoretical and experimental mechanistic study of the process by which actinide dialkyls, Cp2*AnR2 (Cp* = η5-(CH3)5C5, An = Th or U), undergo facile double carbonylation and C=C bond formation to yield monomeric or dimeric Cp2*An2+ complexes of the cis-enediolato ligand, cis-RC(Ō)=C(Ō)R. An electronic structural analysis of the proposed actinide bis(acyl) precursor shows that the most stable structure is that of a 20-electron bis(dihaptoacyl), Cp2*An(η2-COR)2. In contrast, the stable structure for the analogous titanium complex is found to be the 18-electron Ti(η2-COR)(η1-COR) configuration. A significant factor in stabilizing the actinide 20-electron structure is a favorable interaction which can only occur between a bis(dihaptoacyl) C=O donor molecular orbital and a metal f orbital. The molecularity of C=C fusion has been studied experimentally via a crossover experiment in which a 1:1 mixture of Cp2*Th(CH3)2 and Cp2*Th(13CH3)2 is carbonylated. Within experimental error, all butenediolate formation occurs at a single metal center. A theoretical analysis of the intramolecular An(η2-COR)2 → AnOC(CH3)=C(CH3)O reaction process has identified a low-energy pathway beginning from a bis(η2-acyl) in which the coplanar C → O vectors point away from each other. Conrotatory twisting of the two η2-COR ligands occurs in concert with C=C fusion, analogous to the process by which two singlet methylenes undergo coupling to form ethylene. In contrast, N → C(acyl) π-electron donation in the analogous carbamoyls, An(η2-CONR2)2, is calculated to substantially increase the barrier to C=C coupling. Just such a situation is observed experimentally.

Original languageEnglish
Pages (from-to)4467-4476
Number of pages10
JournalJournal of the American Chemical Society
Volume108
Issue number15
Publication statusPublished - 1986

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Actinoid Series Elements
Carbonylation
Actinides
Electrons
Fusion reactions
Metals
Ligands
Molecular orbitals
Titanium
Structural analysis
Ethylene
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Double carbonylation of actinide bis(cyclopentadienyl) complexes. Experimental and theoretical aspects. / Tatsumi, Kazuyuki; Nakamura, Akira; Hofmann, Peter; Hoffmann, Roald; Moloy, Kenneth G.; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 108, No. 15, 1986, p. 4467-4476.

Research output: Contribution to journalArticle

Tatsumi, K, Nakamura, A, Hofmann, P, Hoffmann, R, Moloy, KG & Marks, TJ 1986, 'Double carbonylation of actinide bis(cyclopentadienyl) complexes. Experimental and theoretical aspects', Journal of the American Chemical Society, vol. 108, no. 15, pp. 4467-4476.
Tatsumi, Kazuyuki ; Nakamura, Akira ; Hofmann, Peter ; Hoffmann, Roald ; Moloy, Kenneth G. ; Marks, Tobin J. / Double carbonylation of actinide bis(cyclopentadienyl) complexes. Experimental and theoretical aspects. In: Journal of the American Chemical Society. 1986 ; Vol. 108, No. 15. pp. 4467-4476.
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AB - This contribution presents a theoretical and experimental mechanistic study of the process by which actinide dialkyls, Cp2*AnR2 (Cp* = η5-(CH3)5C5, An = Th or U), undergo facile double carbonylation and C=C bond formation to yield monomeric or dimeric Cp2*An2+ complexes of the cis-enediolato ligand, cis-RC(Ō)=C(Ō)R. An electronic structural analysis of the proposed actinide bis(acyl) precursor shows that the most stable structure is that of a 20-electron bis(dihaptoacyl), Cp2*An(η2-COR)2. In contrast, the stable structure for the analogous titanium complex is found to be the 18-electron Ti(η2-COR)(η1-COR) configuration. A significant factor in stabilizing the actinide 20-electron structure is a favorable interaction which can only occur between a bis(dihaptoacyl) C=O donor molecular orbital and a metal f orbital. The molecularity of C=C fusion has been studied experimentally via a crossover experiment in which a 1:1 mixture of Cp2*Th(CH3)2 and Cp2*Th(13CH3)2 is carbonylated. Within experimental error, all butenediolate formation occurs at a single metal center. A theoretical analysis of the intramolecular An(η2-COR)2 → AnOC(CH3)=C(CH3)O reaction process has identified a low-energy pathway beginning from a bis(η2-acyl) in which the coplanar C → O vectors point away from each other. Conrotatory twisting of the two η2-COR ligands occurs in concert with C=C fusion, analogous to the process by which two singlet methylenes undergo coupling to form ethylene. In contrast, N → C(acyl) π-electron donation in the analogous carbamoyls, An(η2-CONR2)2, is calculated to substantially increase the barrier to C=C coupling. Just such a situation is observed experimentally.

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