Synthesis and Characterization of Homo and Heterobimetallic Complexes with a Dicompartmental Macrocyclic Ligand Containing Propionitrile Pendent Arms

Document Type: Research Article


1 Department of Chemistry , University of Mazandaran, P.O. Box 47416-95447 Babolsar, I.R. IRAN

2 Department of Chemistry, Mohammad Reza Hariri Science Foundation, P.O. Box 47146-38474 Babol, I.R. IRAN


A binuclear macrocyclic ligand containing dissimilar N(amine)2O2 and N(imine)2O2 coordination sites sharing two phenolic oxygen atoms, was prepared by cyclic condensation of dialdehyde precursor L1H2 with 1,3-diaminopropane. The ligand includes two propionitrile pendant arms on the amine nitrogen atoms. The homobimetallic complex [ZnL2Zn(OAc)]PF6 was synthesized by one step procedure. Heterobimetallic complexes [ZnL2M(OAc)]PF6  that M= Cu(II) and Ni(II), were prepared by a trans-metallation reaction. The prepared complexes were characterized on the basis of molar conductance measurement, elemental analysis, IR, NMR and UV-Vis spectroscopy techniques. Characterization results showed that the nitrogen atoms of propionitrile pendant arms are not involved in the coordination to the metal center and also the two metal ions are bridged by two phenolic oxygen atoms and an acetate group.


Main Subjects

[1] Golchoubian H., NematiKharatGhaziani A., Hydrogen Peroxide Oxidation of Mono-and Disubstituted Alkylarenes Catalyzed by DinuclearCoIII-CuII Macrocyclic Complex, Polish J. Chem., 79, p. 825-830 (2005).

[4] 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, p. 2931-2938 (2008).

[5] Yonemura M., Nakamura Y., Usuki N., Ōkawa H., Macrocyclic Effects Upon Isomeric CuIIMII and MIICuII Cores. Formation with Unsymmetric Phenol-Based Macrocyclic Ligands, J. Chem. Sci., 112, p. 291-310 (2000).

[6] Yonemura M., Matsumura Y., Furutachi H., Ohba M., Okawa H., Fenton D.E., Migratory Transmetalation in Diphenoxo-Bridged CuIIMII Complexes of a DinucleatingMacrocycle with N (amine)2O2 and N(imine)2O2 Metal-Binding Sites, Inorg. Chem.,36, p. 2711-2717 (1997).

[8] Fraser C., Johnston L., Rheingold A.L., Haggerty B.S., Williams G. K., Whelan J., Bosnich B., Bimetallic Reactivity, Synthesis, Structure and Reactivity of Homo-and Heterobimetallic Complexes of a BinucleatingMacrocyclic Ligand Containing 6-and 4-Coordination Sites, Inorg. Chem., 31, p. 1835-1845(1992).

[9] McCollum D.G., Hall L., White C., Ostrander R., Rheingold A.L., Whelan J., Bosnich B., Bimetallic Reactivity. Preparation and Characterization of Symmetrical Bimetallic Complexes of a Binucleating Macrocyclic Ligand, Cytim, Containing 6-and 4-Coordinate Sites, Inorg. Chem., 33, p. 924-933(1994).

[13] NiaziRahnama A., Golchoubian H., Pritchard R., Preparation of Monometallic Complexes of Non-Macrocyclic Ligands, Bull. Chem. Soc. Jpn, 78: 1047-1053 (2005).

[17] Yonemura M., Arimura K., Inoue K., Usuki N., Ohba M., Okawa H., Coordination-Position Isomeric MIICuII and CuIIMII (M= Co, Ni, Zn) Complexes Derived from Macrocyclic Compartmental Ligands, Inorg. Chem., 41, p. 582-589 (2002).

[18] Furutachi H., Fujinami S., Suzuki M., Ōkawa H.. DinuclearCoIIMII (M= Pb or Co) Complexes Having a “Co (salen)” Entity in a Macrocyclic Framework: LigandModulation Effect and Neighboring Metal (II) Effect Upon Oxygenation at the “Co (Salen)” Center,J. Chem. Soc. Dalton Trans., 2761-2769 (2000).

[21] Sun G.C., He Z.H., Li Z.J., Yuan X.D., Yang Z.J., Wang G.X., Liu C.R., Facile Synthesis of 1, 6-Bis (2-furyl)-2, 5-bis (2-hydroxy-3-formyl-5-methylbenzyl)-2, 5-diazahexane: a New Dinucleating Ligand, Molecules, 6, p. 1001-1005 (2001).

[23] Robinson J.W., “Practical Handbook of Spectral Data”, Wiley-Interscience: New York (1997).

[24] Silverstein R.M., Bassler G.C., “Spectrometric Identification of Organic Compound”, Wiley & Sons: New York (1988).

[25] Dolphin D.A. Wick,“Tabulation of Infrared Spectral Data”, Wiley-Interscience: New York (1977).

[26] Nakamuta K., “Infrared and Raman Spectra of Inorganic and Coordination Compounds”, 4th Ed., Section II.8. Wiley-Interscience: New York (1988).

[28] Furutachi H., Ishida A., Miyasaka H., Fukita N., Ohba M., Ōkawa H., Koikawa M., FeIIPbII and FeIII Complexes of Macrocyclic Compartmental Ligands: Different Cyclization in Stepwise Template Synthesis Using FeII/PbII or FeIII/PbII pairs, J. Chem. Soc., Dalton Trans., 367-263 (1999).