Transition metal mediated epoxidation as test case for the performance of different density functionals: A computational study

Luigi Cavallo, Heiko Jacobsen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

49 Scopus citations

Abstract

Energy profiles for olefin epoxidation with the cationic [Mn(acacen')]+ catalyst (acacen' = -O(CH)3N-C2H4-N(CH)3O -) have been calculated using pure (BP86) and hybrid (B3LYP) density functional methodologies. For the reaction, triplet and quintet energy hyper surfaces have been considered. The BP86 calculations allow for a rationalization of a reaction occurring under spin conservation. On the other hand, the B3LYP calculations suggest a reaction profile involving an early spin-crossing step, strongly supporting two-state reactivity. Further, the BP86 calculations suggest the existence of a metallacycle as possible reaction intermediate, a proposition not supported by the B3LYP approach. The two different computational approaches result not only in a quantitatively, but also in a qualitatively different description of the epoxidation reaction. This in turn implies different models for chirality transfer associated with related reactions employing chiral catalytic systems.

Original languageEnglish (US)
Pages (from-to)5466-5471
Number of pages6
JournalJournal of Physical Chemistry A
Volume107
Issue number28
DOIs
StatePublished - Jul 17 2003

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Transition metal mediated epoxidation as test case for the performance of different density functionals: A computational study'. Together they form a unique fingerprint.

Cite this