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Issue 5, 2013
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Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

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Abstract

Four dinuclear bis(μ-Cl) bridged copper(II) complexes, [Cu2(μ-Cl)2(LX)2](ClO4)2 (LX = N,N-bis[(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate LX ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1–3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6′-But-biphenyl-3,4,3′,4-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Graphical abstract: Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(ii) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

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Publication details

The article was received on 05 May 2012, accepted on 18 Oct 2012 and first published on 25 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT30983A
Citation: Dalton Trans., 2013,42, 1879-1892
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    Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

    I. Banerjee, P. N. Samanta, K. K. Das, R. Ababei, M. Kalisz, A. Girard, C. Mathonière, M. Nethaji, R. Clérac and M. Ali, Dalton Trans., 2013, 42, 1879
    DOI: 10.1039/C2DT30983A

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