Synthesis, characterization and catalytic oxyfunctionalization of cyclohexene with tert-butylhydroperoxide over a manganese(II) complex covalently anchored to multi-wall carbon nanotubes (MWNTs)

The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, an hydroxyl functionalized manganese(II) Schiff-base has been covalently anchored on modified MWNTs. The new modified MWNTs have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), thermal analysis, UV–Vis, diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The results suggest that the symmetrical Schiff-base; N,N-bis(4-hydroxysalicylidene)-ethylene-1,2-diamine; H2[(OH)2-salen]; is a bivalent anion with tetradentate N2O2 donors derived from the phenolic oxygens and azomethine nitrogens. The formulae was found to be [Mn((OH)2-salen)] for the 1:1 non-electrolytic complex. The multi-wall carbon nanotubes covalently anchored manganese(II) complex ([Mn((OH)2-salen)]@MWNTs) catalyze the oxidation of cyclohexene with TBHP. Oxidation of cyclohexene catalyzed by this complex gave 2-cyclohexene-1-ol, 2-cyclohexene-1-one and 1-(tert-butylperoxy)-2-cyclohexene as the major products. The manganese(II) complex covalently anchored on MWNTs shows significantly higher catalytic activity than [Mn((OH)2-salen)]. The activity of the immobilized catalyst remains nearly the same after three cycles, suggesting the true heterogeneous nature of the catalyst. This catalyst is more selective towards 2-cyclohexene-1-one.

Graphical abstractThe chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, hydroxyl functionalized manganese(II) Schiff-base has been covalently anchored on modified MWNTs. The new modified MWNTs have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), thermal analysis, UV–Vis, diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. Multi-wall carbon nanotubes covalently anchored manganese(II) complex ([Mn((OH)2-salen)]@MWNTs) catalyze the oxidation of cyclohexene with TBHP.Figure optionsDownload full-size imageDownload as PowerPoint slide