HETEROGENIZED POLYMETALLIC CATALYSTS .1. CATALYTIC AIR OXIDATION OF 3,5-DI-T-BUTYLPHENOL BY CU(II) AND FE(III) COMPLEXED TO A POLYPHENYLENEPOLYMER CONTAINING BETA-DI-KETONE AND BETA-TRI-KETONE SURFACE LIGANDS

Catalysis preparation involves the cyclic trimerization polymerization of acetylated aromatics. The polymer is coated on a high surface area support, Celite, and cured to give insoluble high molecular weight po lymer. Reaction of the remaining acetyl end groups with base and methy l acetate gave beta-diketone groups on the surface of the polymer. A s econd reaction with base and methyl acetate places beta-triketones on the surface, The beta-triketones can bind two metal ions in a known ge ometry. The chemically modified surfaces containing beta-diketone and beta-triketone surface ligands were reacted with Cu(OAc)(2) and FeCl3 to give mono- and bi-metallic surface complexes. The oxidation of 3,5- di-t-butylcatechol was studied with all the surfaces. The monometallic catalysts gave only the ortho-quinone as product. The bimetallic cata lysts absorbed about twice as much dioxygen as the monometallic cataly sts and gave ring cleaved products. Both gave induction periods before dioxygen uptake began. With the bimetallic catalysts the dioxygen upt ake stopped at about the ratio: 2 O-2/l catechol. This is twice as muc h dioxygen as that required for ring cleavage so H2O2 may be the dioxy gen reduction product rather than water. The monomeric Cu(OAc)(2) diox ygen uptake curve reached a maximum and then released gas. This could result from Cu(II) catalyzed decomposition of H2O2.