Synthesis of polymer-supported metal-ion complexes and evaluation of their catalytic activities

被引：0

作者：

Gupta, K.C. ^{[1
]}

Sutar, A.K. ^{[1
]}

机构：

[1] Polymer Research Laboratory, Department of Chemistry, Indian Institute of Technology, Roorkee 247 667, India

来源：

Journal of Applied Polymer Science | 2008年 / 108卷 / 06期

关键词：

Polymer-supported transition-metal-ion complexes of the N; N-bis(o-hydroxy acetophenone) propylene-diamine (HPPn) Schiff base were prepared by the complexation of iron(III); cobalt(II); and nickel(II) ions on a polymer-anchored N; N-bis(5-amino-o-hydroxy acetophenone) propylenediamine Schiff base. The complexation of iron(III); and nickel(II) ions on the polymer-anchored HPPn Schiff base was 83.44; 82.92; and; 89.58; wt; respectively; whereas the unsupported HPPn Schiff base showed 82.29; 81.18; and 87.29 wt % complexation of these metal ions. The iron(III) ion complexes of the HPPn Schiff base showed octahedral geometry; whereas the cobalt(II) and nickel(II) ion complexes were square planar in shape; as suggested by spectral and magnetic measurements. The thermal stability of the HPPn Schiff base increased with the complexation of metal ions; as evidenced by thermogravimetric analysis. The HPPn Schiff base showed a weight loss of 51.0 wt % at 500C; but its iron(III); and nickel(II) ion complexes showed weight losses of 27.0; 35.0; and 44.7 wt % at the same temperature. The catalytic activity of the unsupported and supported metal-ion complexes was analyzed by the study of the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The supported HPPn Schiff base complexes of iron(III) ions showed a 73.0 wt % maximum conversion of phenol and 90.6 wt % epoxidation of cyclohexene; but unsupported complexes of iron(III) ions showed 63.8 wt % conversion of phenol and 83.2 wt % epoxidation of cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 wt % and 98.1 wt % with the supported HPPn Schiff base complexes of iron(III) ions; but it was low with the supported Schiff base complexes of cobalt(II) and nickel(II) ions. The selectivity for CTL and ECH varied with the molar ratio of the metal ions but remained unaffected by the molar ratio of hydrogen peroxide to the substrate. The energy of activation for the epoxidation of cyclohexene and oxidation of phenol with the polymer-supported Schiff base complexes of iron(III) ions was 10.0 and 12.7 kJ/mol; but it was found to be higher with the supported HPPn Schiff base complexes of cobalt(II) and nickel(II) ions and with the unsupported HPPn Schiff base complexes of iron(III); and nickel(II) ions. © 2008 Wiley Periodicals; Inc;

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页码：3927 / 3941

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