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Chromium-salen-mediated alkene epoxidation: a theoretical and experimental study indicates the importance of spin-surface crossing and the presence of a discrete intermediate.
2002 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 8, no 18, 4299-307 p.Article in journal (Refereed) Published
Abstract [en]

The mechanism of alkene epoxidation by chromium(v) oxo salen complexes has been studied by DFT and experimental methods. The reaction is compared to the closely related Mn-catalyzed process in an attempt to understand the dramatic difference in selectivity between the two systems. Overall, the studies show that the reactions have many similarities, but also a few critical differences. In agreement with experiment, the chromium system requires a change from low- to high-spin in the catalytic cycle, whereas the manganese system can proceed either with spin inversion or entirely on the high-spin surface. The low-spin addition of metal oxo species to an alkene leads to an intermediate which forms epoxide either with a barrier on the low-spin surface or without a barrier after spin inversion. Supporting evidence for this intermediate was obtained by using vinylcyclopropane traps. The chromium(v) oxo complexes can adopt a stepped shape or form a more concave surface, analogous to previous results on manganese salen complexes.

Place, publisher, year, edition, pages
2002. Vol. 8, no 18, 4299-307 p.
National Category
Organic Chemistry Theoretical Chemistry
URN: urn:nbn:se:uu:diva-233352DOI: 10.1002/1521-3765(20020916)8:18<4299::AID-CHEM4299>3.0.CO;2-BPubMedID: 12298022OAI: oai:DiVA.org:uu-233352DiVA: diva2:768242
Available from: 2014-12-03 Created: 2014-10-02 Last updated: 2016-08-17

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