金属卟啉取代基对其在Lyons系统中催化行为影响.pdfVIP

Journal of Molecular Catalysis A: Chemical 198 (2003) 215–221 The effect of peripheral substituents in metalloporphyrins on their catalytic activity in Lyons system J. Haber∗, L. Matachowski, K. Pamin, J. Poltowicz Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Kraków, Poland Received 11 September 2002; accepted 2 December 2002 Abstract Manganese porphyrin catalysts with different number of halogens atoms substituted at the phenyl and pyrrole rings were investigated in the Lyons system in oxidation of cyclooctane with molecular oxygen (as air) to cyclooctanone and cyclooctanol without the use of sacrificial co-reductant. The catalytic activity of metalloporphyrins increases with the increase of the redox potential of metalloporphyrins in the investigated system and shows almost linear relationship with the number of the halogens on porphyrin macrocycle. On the basis of obtained results the new reaction mechanism is discussed and proposed. © 2002 Elsevier Science B.V. All rights reserved. Keywords: Metalloporphyrins; Hydrocarbon oxidation; Cyclooctane 1. Introduction air), which is an inexpensive, abundant and read- ily available oxidant. These complexes, in particular Metalloporphyrins have in recent years attracted bearing electron-withdrawing substituents at the por- much interest, as they are able to perform selectively phyrin macrocycle, are efficient catalysts for the direct various oxygenation reactions of hydrocarbons in reaction of hydrocarbons with molecular oxygen to liquid phase under mild conditions. They are also give alcohol an