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New non-heme iron model compounds as catalysts in the oxidation of olefins
e iron model compoun @a&s %otxz Qe Laorden, Universitaet Heidelberg, ichae! Merz, Universitaet Heidelberg, Germany Peter Comba, Universitaet Heidelberg, Germany
Germany
Oiehns can be oxidized in the presence of various iron catalysts. Under mild conditions (diluted solutions of II,O,), the main products are ? i = wAJyLH2 I----? aicohois and epoxides. We have performed the reaction under aerobic 3 ‘R’ \---I L6K-i and anaerobic conditions to study the influence of oxygen as oxidant. cn 11111 All ligands used are based on the rigid 3,7-diazabicyclononane backbone. The heteroaromatic substituents RL and R2 are widely varied to investigate steric as we11as eiectronic ~~~~e~~es on electronic properties and reactivities. The immediate oxidation product is an iron(I a% and its stabiii@, reactivity and electronic properties are studied in detail, and correlated with &beligand strut knowledge of the reaction mechanism will allow us to tune the reactivity and selectivity insight in tbe reaction mechanism of biologically active analogs.
ioxygen and water activati University
of Southern
Denmark,
Odense, Denmark
Kenneth B Jensen, University of Southern Denmark, Odense, Denmark Christine 3 McKenzie, University of Southern Denmark, Odense, Denmark cacti-e~ectre~ redox processes, like 0, binding, activation and formation are often supported by more than one transition metal ion in both biological and synthetic systems. A dimanganese(I1) complex of a dinucleating hgand (see crystal structure in figure) reacts with 0, in solution and the solid state In solution, the nature of the oxidized products depends on whether or not solvent oxidation occurs. In acetone, the formation of a co-crystailised product containing formate, and acetate bridging groups, can be explained by an oxidative cleavage of acetone to give the one and two carbon atom precursors require . Trace water is necessary for the reaction. In ‘dry’ solvents a series of dinuclear and tetranuclear complexes, whose topology and total oxidation state is apparently controlled by adventitious water coa~~i~at~on,have been characterized.
Germany
Oiehns can be oxidized in the presence of various iron catalysts. Under mild conditions (diluted solutions of II,O,), the main products are ? i = wAJyLH2 I----? aicohois and epoxides. We have performed the reaction under aerobic 3 ‘R’ \---I L6K-i and anaerobic conditions to study the influence of oxygen as oxidant. cn 11111 All ligands used are based on the rigid 3,7-diazabicyclononane backbone. The heteroaromatic substituents RL and R2 are widely varied to investigate steric as we11as eiectronic ~~~~e~~es on electronic properties and reactivities. The immediate oxidation product is an iron(I a% and its stabiii@, reactivity and electronic properties are studied in detail, and correlated with &beligand strut knowledge of the reaction mechanism will allow us to tune the reactivity and selectivity insight in tbe reaction mechanism of biologically active analogs.
ioxygen and water activati University
of Southern
Denmark,
Odense, Denmark
Kenneth B Jensen, University of Southern Denmark, Odense, Denmark Christine 3 McKenzie, University of Southern Denmark, Odense, Denmark cacti-e~ectre~ redox processes, like 0, binding, activation and formation are often supported by more than one transition metal ion in both biological and synthetic systems. A dimanganese(I1) complex of a dinucleating hgand (see crystal structure in figure) reacts with 0, in solution and the solid state In solution, the nature of the oxidized products depends on whether or not solvent oxidation occurs. In acetone, the formation of a co-crystailised product containing formate, and acetate bridging groups, can be explained by an oxidative cleavage of acetone to give the one and two carbon atom precursors require . Trace water is necessary for the reaction. In ‘dry’ solvents a series of dinuclear and tetranuclear complexes, whose topology and total oxidation state is apparently controlled by adventitious water coa~~i~at~on,have been characterized.