HETEROGENIZED POLYMETALLIC CATALYSTS .2. OXIDATION OF 3,5-DI-T-BUTYLPHENOL BY CU(II), FE(III) AND PD(II) COMPLEXED TO A POLYPHENYLENE POLYMER CONTAINING BETA-DIKETONE AND TRIKETONE SURFACE LIGANDS - AN IMPROVED CATALYST SYSTEM
Pm. Henry et al., HETEROGENIZED POLYMETALLIC CATALYSTS .2. OXIDATION OF 3,5-DI-T-BUTYLPHENOL BY CU(II), FE(III) AND PD(II) COMPLEXED TO A POLYPHENYLENE POLYMER CONTAINING BETA-DIKETONE AND TRIKETONE SURFACE LIGANDS - AN IMPROVED CATALYST SYSTEM, Inorganica Chimica Acta, 240(1-2), 1995, pp. 205-215
Polyphenylene polymer preparation involves the cyclic trimerization po
lymerization of acetylated methyl benzoate with diacetyl benzene. Sinc
e the methyl benzoate groups do not take part in the polymerization th
ey are present in high concentration. The P-diketone ligands were plac
ed on the surface by reaction of the methylbenzoate group with base an
d a methyl ketone and the triketone by reaction with base to give the
beta-triketone. The beta-triketones can bind two metal ions in a known
geometry that is suitable for bimetallic catalysis of the rapid polye
lectron oxidation of catechols. The final catalytic surfaces were prep
ared by treating the chemically modified polymer with copper(II), iron
(II) and palladium(II) acetonitrile complexes with non-coordinating BF
4- as the anion. Since the metal ions contain no strongly coordinating
ligand, they are very reactive species. These surfaces catalyzed the
rapid air oxidation of 3,5-di-tert-butylcatechol (DTBC). The diketone
surfaces gave only 3,5-di-tert-butyl-o-quinone (DTBQ) while the triket
one surfaces gave ring-cleaved products, confirming the special cataly
tic effect of the triketone surface. Also, only the triketone catalyst
s showed any activity for ring cleavage oxidation of DTBQ. These catay
lsts were much more reactive than previous ones using the same polyphe
nylene polymer but without the methyl benzoate groups. With these poly
mers the di- and triketone groups were placed on the surface by chemic
al modification of the unpolymerized acetyl groups.