Olefinepoxidierung mit Methyltrioxorhenium: eine Dichtefunktionalstudie zu Energetik und Mechanismen

Der Angriff des Olefins auf eine Peroxogruppe unter Bildung eines Spiroubergangszustands ist theoretischen Untersuchungen zufolge bei der Epoxidierung von Olefinen mit dem Katalysatorsystem CH3ReO3/H2O2 bevorzugt (siehe Bild). Dieser Befund wird durch Dichtefunktionalrechnungen an mehr als zehn Ubergangszustanden der wahrscheinlichsten Mechanismen gestutzt. Die Hydratisierung hat einen bedeutenden Einflus auf mehrere an der Reaktion beteiligte Spezies: Sie stabilisiert Intermediate und destabilisiert, von einer Ausnahme abgesehen, die Ubergangszustande.

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