Nature 369, 543 - 546 (16 June 1994); doi:10.1038/369543a0

Zeolite-encapsulated Mn(II) complexes as catalysts for selective alkene oxidation

Peter-Paul Knops-Gerrits, Dirk De Vos, Frédéric Thibault-Starzyk & Pierre A. Jacobs^*

Centrum voor Oppervlaktechemie en Katalyse, KU Leuven, Kardinaal Mercierlaan 92, B-3001 Heverlee, Belgium
^* To whom correspondence should be addressed.

COMPLEXES of manganese(ii) with bipyridine (bpy) have the potential to act as catalysts for oxidation of alkanes and alkenes when the complex is oxidized in acidic conditions^1–6. But their catalytic activity in solution is limited by their catalase activity⁷—their tendency to decompose H₂O₂. Because of their polynuclear nature such complexes cannot induce epoxidation of alkenes, and other epoxidation catalysts suffer from self-oxidation and side reactions^8–11. Moreover, all of these homogeneous catalytic processes require phase-transfer conditions. Here we report that, when encapsulated in the supercages of zeolites X and Y, cis-[Mn(bpy)₂]²⁺ complexes can catalyse selective epoxidation of alkenes without complications from competing processes such as self-oxidation or catalase activity. Epoxidation of cycloalkenes is followed by acid-catalysed ring-opening, carbon–carbon bond cleavage and formation of alkenedioic acids (Fig. 1). All of the various intermediates in the process can be obtained selectively by controlling the reaction conditions and zeolite acidity. Thus this supramolecular system provides a clean, one-step heterogeneous catalytic route to useful industrial products.

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