title: Toward a catalytic cycle for the Mn-salen mediated alkene epoxidation: a computational approach.
abstract: BP86 density functional calculations for the title reaction are presented, where a model catalyst with hypochlorite as oxygen-containing counter ligand, (ClO)(O)Mn(acacen') (acacen' = -O(CH)3N-C2H4-N(CH)3O-), is employed. The epoxidation reaction on potential energy surfaces corresponding to an overall spin-density of two and four unpaired electrons is investigated. The presence of the hypochlorite ligand is found to cause the reaction to proceed under conservation of spin. Further, the oxygen-containing counter ligand causes reoxidation of the Mn-center, thus closing the catalytic cycle. A catalytic scheme is therefore proposed, which includes a step of regeneration of the catalytically active species. Energetic estimates including corrections for solvent effects are presented for the relevant steps constituting the proposed catalytic scheme.
authors.affiliation: Department of Chemistry, Università di Salerno, Via Salvador Allende, Baronissi (SA) I-84081, Italy.
authors.forename: Luigi
authors.initials: L
authors.lastname: Cavallo
authors.forename: Heiko
authors.initials: H
authors.lastname: Jacobsen