Electronic effects in (salen)Mn-based epoxidation catalysts

Luigi Cavallo, Heiko Jacobsen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

99 Scopus citations


Presented are density functional calculations on various Mn(salen) systems that are active catalysts in the epoxidation of olefins. Correlation of various structural properties such as Mn=O bond strengths, atomic charges, and C-O distances of evolving bonds in transition state geometries with modified Hammett constants reveal a mechanistic picture of the epoxidation reaction, supporting previous experimental results. Enantioselectivity is tied to the position of a transition state along the reaction coordinate for the first C-O bond formation step, when an olefin is approaching the epoxidation catalyst. Electronic effects exhibited by the 5,5′ substituents of the salen ligand manifest themselves in a tuning of the Mn=O bond strength, which in turn influences the C-O distance of the forming bond in the transition state geometry.

Original languageEnglish (US)
Pages (from-to)6202-6207
Number of pages6
JournalJournal of Organic Chemistry
Issue number16
StatePublished - Aug 8 2003

ASJC Scopus subject areas

  • Organic Chemistry


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