Toward a Catalytic Cycle for the Mn-Salen Mediated Alkene Epoxidation: A Computational Approach

Luigi Cavallo, Heiko Jacobsen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

50 Scopus citations

Abstract

BP86 density functional calculations for the title reaction are presented, where a model catalyst with hypochlorite as oxygen-containing counter ligand, (ClO)(O)Mn(acacen′) (acacen′ = -O(CH)3N-C 2H4-N(CH)3O-), is employed. The epoxidation reaction on potential energy surfaces corresponding to an overall spin-density of two and four unpaired electrons is investigated. The presence of the hypochlorite ligand is found to cause the reaction to proceed under conservation of spin. Further, the oxygen-containing counter ligand causes reoxidation of the Mn-center, thus closing the catalytic cycle. A catalytic scheme is therefore proposed, which includes a step of regeneration of the catalytically active species. Energetic estimates including corrections for solvent effects are presented for the relevant steps constituting the proposed catalytic scheme.

Original languageEnglish (US)
Pages (from-to)2175-2182
Number of pages8
JournalInorganic Chemistry
Volume43
Issue number6
StatePublished - Mar 22 2004

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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