Abstract
In this work, we investigated the preparation of P450-bioinspired Mn(iii)-Schiff base complexes supported on DEAE-cellulose ((R,R)-Jacobsen/Cell(NEt(2)) and (S,S)-Jacobsen/Cell(NEt(2)), respectively) to oxidize substrates of biological interest. Catalysts were characterized by several physical techniques. UV-Vis spectroscopy with diffuse reflectance (DR/UV-Vis) analysis featured peculiar electronic transitions for both complexes. Fourier transform infrared (FTIR) spectra evidenced the characteristic band of imine groups (HC[double bond, length as m-dash]N) for bioinspired/Cell(NEt(2)) materials. Immobilization ratios in cellulose fibres were confirmed by atomic absorption spectroscopic (GF-AAS) analyses. Catalytic essays were conducted during rhodamine B (RhB) oxidation. Supported materials attained oxidative yields close to those of homogeneous systems, and cellulose may be stabilizing the active intermediate catalytic species. Reactions may be driven through two different intermediates: Mn(V)(O) and Mn(III)(O-OH)salen. Homogeneous reactions suggest an asymmetric catalysis. Heterogeneous system reaction yields are similar, and salen complexes anchored on cellulose conformation would interfere on complex intermediate species configuration. The four possible RhB-oxidation products obtained by the reaction with the homogeneous (S,S)-Jacobsen catalyst and meta-chloroperoxybenzoic acid (m-CPBA) system were suggested by (1)H NMR analysis, and a catalytic mechanism was proposed.