Electronic effects in (salen)Mn-based epoxidation catalysts

Luigi Cavallo, Heiko Jacobsen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

95 Scopus citations

Abstract

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
Volume68
Issue number16
DOIs
StatePublished - Aug 8 2003

ASJC Scopus subject areas

  • Organic Chemistry

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