Supported tetra(-4-pyridyl)porphyrinato-manganese(III) [MnIII(TPyP)]+ and -tin(IV) [SnIV(TPyP)]2+ have been prepared. The solid support was iodonated poly(siloxane) surface prepared by condensation reactions of (EtO)4Si with (MeO)3Si(CH2)3I. The supported metalloporphyrins were employed as catalysts for the oxidation reactions of 1-octene and of cyclohexene. NaBH4 was used to reduce [MnIII(TPyP)]+ and [SnIV(TPyP)]2+ back to their catalytically active MnII and SnII forms, respectively. Contrary to their homogeneous counterparts, both of the supported metalloporphyrins catalysed the cyclohexene oxidation reaction to yield only 2-cyclohexen-1-one with no other products over a reaction time of 10 h. In addition to cyclohexene oxidation, the supported [MnIII(TPyP)]+ catalysed 1-octene oxidation as well, whereas the supported [SnIV(TPyP)]2+ was inactive for the oxidation of 1-octene.

Journal of Molecular Catalysis A: Chemical, Volume 113, Issues 1-2, 25 November 1996, Pages 35-44