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Synthesis, electrochemical, magnetic, catalytic and antimicrobial studies of N-functionalized cyclam based trinuclear copper(II) and nickel(II) complexes

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Abstract

Trinuclear copper(II) and nickel(II) complexes have been prepared by using Schiff base ligands derived from 1,8-[bis(3-formyl-2-hydroxy-5-methyl) benzyl]-4,11-dimethyl-l,4,8,11-tetraazacyclotetradecane, and 1,8-[bis(3-formyl-2-hydroxy-5-bromo)benzyl]-4,11-dimethyl-l,4,8,11-tetraazacyclotetradecane with aliphatic and aromatic diamines. All the complexes were characterized by elemental and spectroscopic analysis. Electrochemical studies of the copper(II) complexes in DMF solution show three irreversible one electron reduction process around E 1pc  = −0.59 to −0.80 V, E 2pc  = −0.89 to −1.14 V and E 3pc  = −1.17 to −1.29 V, and for nickel(II) complexes it is around E 1pc  = −0.63 to −0.77 V, E 2pc  = −1.20 to −1.35 V and E 3pc  = −1.60 to −1.74 V. ESR spectra and magnetic moments of the trinuclear Cu(II) complexes show the presence of antiferromagnetic coupling. Cryomagnetic investigation of the trinuclear copper(II) complexes show that the observed −2J values are in the range of 116–178 cm−1. The rate constants for hydrolysis of 4-nitrophenylphosphate by the complexes are in the range of 2.68 × 10−2 to 9.81 × 10−2 min−1. The rate constants values for the catecholase activity of the copper(II) complexes fall in the range of 3.03 × 10−2 to 9.32 × 10−2 min−1. All the complexes.

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References

  1. Hancock, R.D., Maumela, H., Desousa, A.S.: Macrocyclic ligands with pendent amide and alcoholic oxygen donor groups. Coord. Chem. Rev. 148, 315 (1996)

    Article  CAS  Google Scholar 

  2. Hegg, E.L., Burstyn, J.N.: Toward the development of metal-based synthetic nucleases and peptidases: a rationale and progress report in applying the principles of coordination chemistry. Coord. Chem. Rev. 173, 133 (1998)

    Article  CAS  Google Scholar 

  3. Bradshaw, J.S.: Aza-crown Macrocycles. Wiley, New York (1993)

    Google Scholar 

  4. Lehn, J.M.: Supramolecular Chemistry. VCH, New York (1995)

    Book  Google Scholar 

  5. Lindoy, L.F.: The Chemistry of Macrocyclic Ligand Complexes. Cambridge University Press, Cambridge, UK (1993)

    Google Scholar 

  6. Sorrell, T.N.: Synthetic models for binuclear copper proteins. Tetrahedron 45, 3 (1989)

    Article  CAS  Google Scholar 

  7. Solomon, E.I., Tuczek, F., Root, D.E., Brown, C.A.: Spectroscopy of binuclear dioxygen complexes. Chem. Rev. 94, 827 (1994)

    Article  CAS  Google Scholar 

  8. Kitajima, N., Moro-oka, Y.: Copper-dioxygen complexes. Inorganic and bioinorganic perspectives. Chem. Rev. 94, 737 (1994)

    Article  CAS  Google Scholar 

  9. Duff, J.C.: A new general method for the preparation of o-hydroxyaldehydes from phenols and hexamethylenetetramine. J. Chem. Soc. 547 (1941)

  10. Lambert, E., Chabut, B., Noblat, S.C., Deronzier, A., Chottard, G., Bousseksou, A., Tuchagues, J.-P., Laugier, J., Dardet, M., Latour, J.-M.: Synthesis, structural, magnetic, and redox properties of asymmetric diiron complexes with a single terminally bound phenolate ligand. Relevance to the purple acid phosphatase enzymes. J. Am. Chem. Soc. 119, 9424 (1997)

    Article  CAS  Google Scholar 

  11. Royal, G., Gindrey, V.D., Dahaowi, S., Tabard, A., Guilard, R., Pullumbi, P., Lecomte, C.: New synthesis of trans-disubstituted cyclam macrocycles—elucidation of the disubstitution mechanism on the basis of X-ray data and molecular modeling. Eur. J. Org. Chem. 1971 (1998)

  12. Gayathri, D., Velmurugan, D., Ravikumar, K., Sreedaran, S., Narayanan, V.: 1,8-Bis(3-formyl-5-methyl-2-oxidobenzyl)-1,8-diaza-4,11-diazoniacyclotetradecane chloroformsolvate. Acta. Crystallogr. E62, o3714 (2006)

  13. Saravanakumar, D., Sengottuvelan, N., Priyadarshni, G., Kandaswamy, M., Okawa, H.: Synthesis of unsymmetrical ‘end-off’ phenoxo and oximinato di bridged copper(II) and nickel(II) complexes: spectral, electrochemical and magnetic properties. Polyhedron 23, 665 (2004)

    Article  CAS  Google Scholar 

  14. Sreedaran, S., Bharathi, K.S., Rahiman, A.K., Jagadish, L., Kaviyarasan, V., Narayanan, V.: Novel unsymmetrical macrocyclic dicompartmental binuclear copper(II) complexes bearing 4- and 6-coordination sites: electrochemical, magnetic, catalytic and antimicrobial studies. Polyhedron 27, 2931 (2008)

    Article  CAS  Google Scholar 

  15. Sreedaran, S., Bharathi, K.S., Rahiman, A.K., Rajesh, K., Nirmala, G., Jagadish, L., Kaviyarasan, V., Narayanan, V.: Synthesis, electrochemical, catalytic and antimicrobial activities of novel unsymmetrical macrocyclic dicompartmental binuclear nickel(II) complexes. Polyhedron 27, 1867 (2008)

    Article  CAS  Google Scholar 

  16. Sreedaran, S., Bharathi, K.S., Rahiman, A.K., Prabu, R., Jegaeesh, R., Raaman, N., Narayanan, V.: N-functionalised cyclam based trinuclear copper(II) complexes: electrochemical, magnetic, catalytic and antimicrobial studies. Trans. Met. Chem. 34, 33 (2009)

    Article  CAS  Google Scholar 

  17. Srinivas, B., Arulsamy, N., Zacharias, P.S.: Catalytic and magnetic properties of a new series of binuclear copper(II) complexes. Polyhedron 10, 731 (1991)

    Article  CAS  Google Scholar 

  18. Fraser, C., Bosnich, B.: Catecholase activity of a series of dicopper(II) complexes with variable Cu-OH(phenol) moieties. Inorg. Chem. 41, 1788 (2002)

    Article  Google Scholar 

  19. Volkmer, D., Hommerich, B., Griesar, K., Haase, W., Krebs, B.: Dinuclear nickel(II) complexes as models for the active site of urease. Inorg. Chem. 35, 3792 (1996)

    Article  CAS  Google Scholar 

  20. Okawa, H., Tadokora, M., Aratake, T.Y., Ohba, M., Shindom, K., Mitsumi, M., Koikawa, M., Tomono, M., Fenton, D.E.: Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles. J. Chem. Soc., Dalton Trans. 253 (1993)

  21. Bleany, B., Bowers, K.D.: Proc. R. Soc. Lond., Ser. A 214, 415 (1952)

    Google Scholar 

  22. Amudha, P., Akilan, P., Kandaswamy, M.: Synthesis, spectral, electrochemical and magnetic properties of new phenoxo-bridged dicopper(II) complexes derived from unsymmetrical binucleating ligands with imino and amino side arms. Polyhedron 19, 1769 (2000)

    Article  CAS  Google Scholar 

  23. Thompson, L.K., Mandal, S.K., Tandon, S.S., Bridson, J.N., Park, M.K.: Magnetostructural correlations in bis(μ2-phenoxide)-bridged macrocyclic dinuclear copper(II) complexes. Influence of electron-withdrawing substituents on exchange coupling. Inorg. Chem. 35, 3117 (1996)

    Article  CAS  Google Scholar 

  24. Mac Lachlan, M.J., Park, M.K., Thompson, L.K.: Coordination compounds of Schiff-base ligands derived from diaminomaleonitrile (DMN): mononuclear, dinuclear, and macrocyclic derivatives. Inorg. Chem. 35, 5492 (1996)

    Article  CAS  Google Scholar 

  25. Lintvedt, R.L., Kramer, L.S.: Reversible sequential transfer of two electrons at the same potential in bis(1, 3, 5-triketonato)dicopper(II) complexes and their diamine Schiff bases. Effect of sodium(+) and similar ions on the cyclic voltammetry. Inorg. Chem. 22, 796 (1983)

    Article  CAS  Google Scholar 

  26. Gagne, R.R., Spiro, C.L., Smith, T.J., Hamann, C.A., Shiemke, A.K.: The synthesis, redox properties, and ligand binding of heterobinuclear transition-metal macrocyclic ligand complexes. Measurement of an apparent delocalization energy in a mixed-valent copper(I)copper(II) complex. J. Am. Chem. Soc. 103, 4073 (1981)

    Article  CAS  Google Scholar 

  27. Mishra, A.K., Dogra, S.K.: Effects of solvents and pH on the spectral behavior of 2-(p-Aminophenyl)benzimidazole. Bull. Chem. Soc. Jpn. 58, 3587 (1985)

    Article  CAS  Google Scholar 

  28. Bailey, N.A., Fenton, D.E., Lay, J., Roberts, P.B., Latour, J.M., Limosin, D.: Magnetic and electrochemical studies on binuclear copper(II) complexes derived from 2,6-diacetyl-4-methylphenol: the X-ray and molecular structure of an acyclic, binuclear Schiff-base complex. J. Chem. Soc., Dalton Trans. 2681 (1986)

  29. Alexander, V.: Design and synthesis of macrocyclic ligands and their complexes of lanthanides and actinides. Chem. Rev. 95, 273 (1995)

    Article  CAS  Google Scholar 

  30. Karunakaran, S., Kandaswamy, M.: Synthesis, electrochemical and magnetic properties of a series of new unsymmetrical macrocyclic binuclear copper(II) complexes. J. Chem. Soc., Dalton. Trans. 1595 (1994)

  31. Bharathi, K.S., Sreedaran, S., Rahiman, A.K., Rajesh, K., Narayanan, V.: Synthesis, spectral, magnetic, electrochemical and kinetic studies of copper(II), nickel(II) and zinc(II) acetate complexes derived from phenol based ‘end-off’ ligands: effect of p-substituents. Polyhedron 26, 3993 (2007)

    Article  CAS  Google Scholar 

  32. Roy, T.G., Hazari, S.K.S., Dey, B.K., Miah, H.A., Bader, C., Rehder, D.: Copper(II) and nickel(II) complexes of N,N-bis(2-hydroxyethyl)octamethyl-1,4,8,11-tetraazacyclotetradecane. Eur. J. Inorg. Chem. 4115 (2004)

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Acknowledgments

Financial support from University Grants Commission (RGN-JRF), New Delhi, is gratefully acknowledged. We are thankful to CDRI-Lucknow for providing FAB Mass spectral analysis.

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Authors and Affiliations

  1. Department of Inorganic Chemistry, School of Chemical Sciences, University of Madras, Guindy Campus, Chennai, 600 025, India

    S. Sreedaran, K. Shanmuga Bharathi, A. Kalilur Rahiman & V. Narayanan

  2. Centre for Advanced Studies in Botany, University of Madras, Guindy Campus, Chennai, 600 025, India

    L. Jagadish & V. Kaviyarasan

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  1. S. Sreedaran
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  2. K. Shanmuga Bharathi
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  3. A. Kalilur Rahiman
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  6. V. Narayanan
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Correspondence to V. Narayanan.

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Sreedaran, S., Bharathi, K.S., Rahiman, A.K. et al. Synthesis, electrochemical, magnetic, catalytic and antimicrobial studies of N-functionalized cyclam based trinuclear copper(II) and nickel(II) complexes. J Incl Phenom Macrocycl Chem 66, 297–306 (2010). https://doi.org/10.1007/s10847-009-9621-y

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