Organoactinides promote the dimerization of aldehydes: Scope, kinetics, thermodynamics, and calculation studies

Manab Sharma, Tamer Andrea, Nigel J. Brookes, Brian F. Yates, Moris S. Eisen

Research output: Contribution to journalArticlepeer-review

55 Scopus citations

Abstract

Surprising catalytic activities have been found for the actinide complexes Cp*2ThMe2 (1), Th(NEtMe)4 (2), and Me2SiCp″2Th(C4H9) 2(3) toward oxygenated substrates. During the catalytic dimerization of benzaldehydes to their corresponding esters, complexes 1 and 2 gave 65 and 85% yield in 48 h, respectively, while the geometry-constrained complex 3 gave 96% yield in 24 h. Exploring the effect of substituents on benzaldehyde, it has been found that, in general, electron-withdrawing groups facilitate the reaction. Kinetic study with complexes 1 and 3 reveals that the rate of the reaction is first order in catalyst and substrate, which suggests the rate equation "rate = k[catalyst]1[aldehyde]1". The activation energy of the reaction was found to be 7.16 ± 0.40 and 3.47 ± 0.40 kcal/mol for complexes 1 and 3 respectively, which clearly indicates the advantage of the geometry-constrained complex. Astonishing are the reactivity of the organoactinide complexes with oxygen-containing substrates, and especially the reactivity of complex 3, toward the dimerization of substrates like p-methoxybenzaldehyde, m/p-nitrobenzaldehyde, and furanaldehyde and the reactivity toward the polymerization of terephthalaldehyde. Density functional theory mechanistic study reveals that the catalytic cycle proceeds via an initially four-centered transition state (+6 kcal/mol), followed by the rate-determining six-centered transition state (+13.5 kcal/mol), to yield thermodynamically stable products.

Original languageEnglish
Pages (from-to)1341-1356
Number of pages16
JournalJournal of the American Chemical Society
Volume133
Issue number5
DOIs
StatePublished - 9 Feb 2011
Externally publishedYes

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