Organocatalytic activity of [3]ferrocenophanes: a computational study

Dániel Buzsáki, Zsolt Kelemen, L. Nyulászi

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The organocatalytic activity of the recently synthesized diamino[3]ferrocenophanes and the related thioamino[3]ferrocenophane was investigated in the benzoin condensation computationally. The nucleophilicity of these compounds is slightly increased compared to the imidazolidin-2-ylidene, as a consequence of the increased bond angle at the carbene center. Among the possible isomers of the carbene–aldehyde adducts, we have located a hitherto unexplored structure with an oxirane moiety. The isomers of the related carbene–aldehyde adducts including the Breslow intermediates have similar stability in comparison with the imidazolidin-2-ylidene and thiazolidin-2-ylidene, respectively; moreover, the barriers of the interconversion of these adducts are also similar; however, the oxirane-type compound formed from benzaldehyde and the diamino[3]ferrocenophane is significantly stabilized with respect to its isomers. The barrier of the addition of the second aldehyde to the Breslow intermediate increased by 9–15 kcal/mol in case of the [3]ferrocenophanes compared to the 5-membered analogues, which could partly be explained by the higher stabilization of the van der Waals adduct of the Breslow intermediate and the second aldehyde. Since the addition of the second aldehyde is blocked, these carbenes could be suitable for the experimental investigation of the carbene–aldehyde adducts.

Original languageEnglish
Pages (from-to)1-8
Number of pages8
JournalStructural Chemistry
DOIs
Publication statusAccepted/In press - Jul 5 2016

Keywords

  • Benzoin condensation
  • Carbene
  • DFT
  • Ferrocenophane

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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