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Syntheses, structures and catalytic activities of dinuclear copper complexes with tetradentate diaminebis (phenolate) ligands

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Abstract

Two new Cu(II) complexes were synthesized from Cu(NO3)2·3H2O and salan ligands, H2[H4]L1 and H2[H4]L2 (H2[H4]L1 = N,N′-bis(o-hydroxybenzyl)-1,2-diaminocyclohexane; H2[H4]L2 = N,N′-bis(o-hydroxybromobenzyl)1,2-diaminocyclohexane). They were characterized by various spectroscopic methods and structures of the complexes determined by X-ray diffraction analyses. Interestingly, H2[H4]L1 coordinates to copper centers as monoanionic in a tetradentate mode in complex 1, [Cu(H[H4]L1)]2·2NO3·2H2O, whereas H2[H4]L2 behaves as a dianionic ligand in complex 2, [Cu([H4]L2)]2·0.4H2O, via the O,N,N′,O′-donor atoms. The asymmetric unit in the complexes is dimerized about a center of inversion by asymmetric bridging of the phenoxide-O atom between two metal centers. The electronic spectra studies of the complexes in various solvents with different coordination numbers proved the stability of the dinuclear complexes in solvents other than DMSO and DMF. Complexes 1 and 2 showed high catalytic activities with good-to-excellent selectivities in the oxidation of olefins, benzyl alcohol and ethyl benzene with H2O2 in acetonitrile. A probable mechanism is discussed.

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Acknowledgments

The authors wish to thank Professor T. Lis for data collection and preliminary structure solving. The authors are grateful to the University of Zanjan, University of Warsaw and Ludwig-Maximilians-Universität for financial assistance.

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Authors and Affiliations

  1. Department of Chemistry, University of Zanjan, 45195-313, Zanjan, Islamic Republic of Iran

    Hassan Hosseini-Monfared & Susan Soleymani-Babadi

  2. Chemistry Department, University of Warsaw, Pasteura 1, 02093, Warsaw, Poland

    Aleksandra Pazio & Krzysztof Wozniak

  3. Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383, Wroclaw, Poland

    Milosz Siczek

  4. Fakultät für Chemie und Pharmazie, Ludwig-Maximilians-Universität, München, Butenandtstr. 5-13, Haus D, 81377, Munich, Germany

    Peter Mayer

  5. Department of Pharmaceutical Biomaterials, School of Pharmacy, Zanjan University of Medical Science, Zanjan, Islamic Republic of Iran

    Somayeh Sadighian

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  1. Hassan Hosseini-Monfared
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  2. Susan Soleymani-Babadi
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Correspondence to Hassan Hosseini-Monfared.

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Hosseini-Monfared, H., Soleymani-Babadi, S., Sadighian, S. et al. Syntheses, structures and catalytic activities of dinuclear copper complexes with tetradentate diaminebis (phenolate) ligands. Transition Met Chem 40, 255–267 (2015). https://doi.org/10.1007/s11243-015-9913-6

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  • DOI: https://doi.org/10.1007/s11243-015-9913-6

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