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Issue 39, 2014
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Synthesis, structure, and catecholase activity of bispyrazolylacetate copper(ii) complexes

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Abstract

A series of six-coordination copper(II) complexes containing bis(3,5-di-t-butylpyrazol-1-yl)acetate (bdtbpza) and N-heterocycles or chelating aliphatic ligands have been synthesized. The steric bulkiness of bis(pyrazol-1-yl)acetate anchors two bdtbpza to situate a trans position and to adopt an O-bound monodentate coordination mode with other nitrogen bases occupying the basal plane. Five mononuclear mixed ligand complexes, [Cu(bdtbpza)2(py)4] 1, [Cu(bdtbpza)2(t-Bupy)4] 2, [Cu(bdtbpza)2(pym)2(MeOH)2] 3, [Cu(bdtbpza)2(eda)2] 4, [Cu(bdtbpza)2(tmeda)(H2O)2] 5, where py = pyridine, t-Bupy = tert-butylpyridine, pym = pyrimidine, eda = ethylenediamine, and tmeda = tetramethylethylenediamine, were isolated and thoroughly characterized. Intriguingly, the heteroleptic complex 5, which has two aquo-ligands oriented in the cis positions, demonstrates higher catecholase-like activity in performing aerial oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylquinone (3,5-DTBQ) than other bis(pyrazolyl)acetate-embedded copper complexes reported herein, which suggests the essential role of labile cis-aquo ligands to promote the catalytic reaction.

Graphical abstract: Synthesis, structure, and catecholase activity of bispyrazolylacetate copper(ii) complexes

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Supplementary files

Article information


Submitted
19 May 2014
Accepted
30 Jul 2014
First published
30 Jul 2014

Dalton Trans., 2014,43, 14726-14736
Article type
Paper
Author version available

Synthesis, structure, and catecholase activity of bispyrazolylacetate copper(II) complexes

M. J. Gajewska, W. Ching, Y. Wen and C. Hung, Dalton Trans., 2014, 43, 14726
DOI: 10.1039/C4DT01467G

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