Synthesis, characterisation and catalytic activities of manganese(III) complexes of pyridoxal-based ONNO donor tetradenatate ligands

Reaction of MnII(CH3COO)2 with dibasic tetradentate ligands, N,N′-ethylenebis(pyridoxylideneiminato) (H2pydx-en, I), N,N′-propylenebis(pyridoxylideneiminato) (H2pydx-1,3-pn, II) and 1-methyl-N,N′-ethylenebis(pyridoxylideneiminato) (H2pydx-1,2-pn, III) followed by aerial oxidation in the presence of LiCl gives complexes [MnIII(pydx-en)Cl(H2O)] (1) [MnIII(pydx-1,3-pn)Cl(CH3OH)] (2) and [MnIII(pydx-1,2-pn)Cl(H2O)] (3), respectively. Crystal and molecular structures of [Mn(pydx-en)Cl(H2O)] (1) and [Mn(pydx-1,3-pn)Cl(CH3OH)] (2) confirm their octahedral geometry and the coordination of ligands through ONNO(2-) form. Reaction of manganese(II)-exchanged zeolite-Y with these ligands in refluxing methanol followed by aerial oxidation in the presence of NaCl leads to the formation of the corresponding zeolite-Y encapsulated complexes, abbreviated herein as [MnIII(pydx-en)]-Y (4), [MnIII(pydx-1,3-pn)]-Y (5) and [MnIII(pydx-1,2-pn)]-Y (6). These encapsulated complexes are used as catalysts for the oxidation, by H2O2, of methyl phenyl sulfide, styrene and benzoin efficiently. Oxidation of methyl phenyl sulfide under the optimized reaction conditions gave ca. 86% conversion with two major products methyl phenyl sulfoxide and methyl phenyl sulfone in the ca. 70% and 30% selectivity, respectively. Oxidation of styrene catalyzed by these complexes gave at least five products namely styrene oxide, benzaldehyde, benzoic acid, 1-phenylethane-1,2-diol and phenylacetaldehyde with a maximum of 76.9% conversion of styrene by 4, 76.3% by 5 and 76.0% by 6 under optimized conditions. The selectivity of the obtained products followed the order: benzaldehyde > benzoic acid > styrene oxide > phenylacetaldehyde > 1-phenylethane-1,2-diol. Similarly, ca. 93% conversion of benzoin was obtained by these catalysts, where the selectivity of the products followed the order benzil > benzoic acid > benzaldehyde-dimethylacetal. Tests for the recyclability and heterogeneity of the reactions have also been carried. Neat complexes are equally active. However, the recycle ability of encapsulated complexes makes them better over neat ones.

Graphical abstractManganese(III) complexes of three ligands derived from pyridoxal and diamines are encapsulated in the cavity of zeolite-Y and catalytic activities for the oxidation, by H2O2, of methyl phenyl sulfide, styrene and benzoin are reported.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Manganese(III) complexes of three ONNO donor ligands have been reported. ► Structures of two complexes have been confirmed by single crystal X-ray study. ► These complexes have also been encapsulated in the nano cavity of zeolite-Y. ► Catalytic potentials of encapsulated complexes for oxidation have been reported.