title: Porphyrin-kaolinite as efficient catalyst for oxidation reactions.
abstract: The preparation, characterization, and application in oxidation reactions of new biomimetic catalysts are reported. Brazilian Sao Simao kaolinite clay has been functionalized with [meso-tetrakis(pentafluorophenyl)porphinato]iron(III), Fe(TPFPP). To obtain the functionalized clay, the natural clay was purified by dispersion-sedimentation, expanded by insertion of dimethyl sulfoxide (DMSO), and functionalized with amino groups by substitution of DMSO with ethanolamine. These previous steps allowed clay functionalization with Fe(TPFPP), leading to a layered material with a basal spacing of 10.73 A. Clay functionalization with the porphyrin was confirmed by formation of the secondary amine, as demonstrated by FTIR bands at 3500-3700 cm(-1). UV-vis spectroscopy revealed a red shift in the Soret band of the iron porphyrin in the functionalized material as compared to the parent iron porphyrin catalyst in solution, indicating Fe(III)P --> Fe(II)P reduction. The catalytic performance of the functionalized clay was evaluated in the epoxidation of cyclooctene, with complete selectivity for the epoxide (100% epoxide yield), and ketonization of cyclohexane, cyclohexanone being the major product. The novel catalyst was also evaluated in the Baeyer-Villiger (BV) oxidation of cyclohexanone, with 85% conversion of cyclohexanone in epsilon-caprolactone, with total selectivity to epsilon-caprolactone.
authors.affiliation: Universidade de Franca, Franca-SP, Brazil.
authors.forename: Natalia
authors.initials: N
authors.lastname: Bizaia
authors.forename: Emerson H
authors.initials: EH
authors.lastname: de Faria
authors.forename: Gustavo P
authors.initials: GP
authors.lastname: Ricci
authors.forename: Paulo S
authors.initials: PS
authors.lastname: Calefi
authors.forename: Eduardo J
authors.initials: EJ
authors.lastname: Nassar
authors.forename: Kelly A D F
authors.initials: KA
authors.lastname: Castro
authors.forename: Shirley
authors.initials: S
authors.lastname: Nakagaki
authors.forename: Katia J
authors.initials: KJ
authors.lastname: Ciuffi
authors.forename: Raquel
authors.initials: R
authors.lastname: Trujillano
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Vicente
authors.forename: Antonio
authors.initials: A
authors.lastname: Gil
authors.forename: Sophia A
authors.initials: SA
authors.lastname: Korili