期刊
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
卷 310, 期 1-2, 页码 34-41出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/j.molcata.2009.05.016
关键词
Catecholase activity; Copper(II); Macrocyclic complexes; Schiff-bases; Template synthesis
Five dinuclear copper(II) complexes, [Cu2L1(N-3)(2)center dot 2H(2)O] (1), [Cu2L2(N-3)(2)center dot 2H(2)O] (2), [Cu2L3(N-3)(2)center dot 2H(2)O] (3), [Cu2L4(N-3)(2)center dot 2H(2)O] (4) and [Cu2L5(N-3)(2)center dot 2H(2)O] (5) of Robson type macrocyclic Schiff-base ligands derived from [2+2] condensation of 4-methyl-2,6-diformylphenol with 1,3-diaminopropane (H2L1), 1,2-diaminoethane (H2L2), 1,2-diaminopropane (H2L3), 1,2-diamino-2-methylpropane (H2L4) and 1.2-diaminocyclohexane (H2L5), respectively have been synthesized and characterized. Catecholase activity of those complexes using 3,5-di-tert-butylcatechol as substrate has been investigated in two solvents, methanol and acetonitrile. The role of the solvent and of the steric properties of the macrocyclic ligand of these complexes on their catecholase activity has been examined thoroughly. Acetonitrile is observed to be a better solvent than methanol as far as their catalytic activity is concerned. However, methanol reveals to be a better choice to identify the enzyme-substrate adduct. The investigation also prompted that chelate ring size does affect on the catalytic efficiency: 6-membered ring (as in H2L1) exhibits better activity than its 5-membered counterpart (as in H2L2). The activity of the 5-membered counter parts also depend upon the steric factor. Moreover, the catalytic activity of the complexes is enhanced to a significant extent by increasing the bulkiness of the substituents on the backbone of macrocyclic H2L2 ligands. (C) 2009 Elsevier B.V. All rights reserved.
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