title: Synthesis and characterization of new unsymmetrical 'side-off' tetra and hexa coordinate homobinuclear Cu(II) and heterobinuclear Cu(II)-Zn(II) complexes: Magnetic, electrochemical and kinetic studies.
abstract: A new class of phenol based unsymmetrical side-off tetra and hexa coordinate homobinuclear Cu(II) and heterobinuclear Cu(II)-Zn(II) complexes have been synthesized and characterized by elemental and spectral analysis. The electronic spectra of all the complexes show "Red shift" in LMCT band, for the ligand H(2)L(2) compared to that of the ligand H(2)L(1) due to the relatively higher electron donating nature of their substitutents. The homobinuclear Cu(II) complexes (1 and 2) illustrate an antiferromagnetic interaction (μ(eff): 1.58 and 1.60BM) at 298K with a broad EPR signal. Variable temperature magnetic moment study of the binuclear copper (II) complexes shows that the extent of antiferromagnetic coupling is greater in the case of H(2)L(2) complexes than H(2)L(1) complexes (-2J values: 192cm(-1) and 184cm(-1) respectively). The heterobinuclear Cu(II)-Zn(II) complexes (3 and 4) have a magnetic moment value close to the spin only value with four hyperfine EPR signals. Electrochemical studies of the complexes reveal that all the binuclear complexes show two irreversible one-electron transfer reduction waves in the cathodic region. There is an "anodic shift" in the first reduction potential of the complexes, of the ligand H(2)L(1) when compared to that of the ligand H(2)L(2) due to the presence of relatively higher electron donating N-substituents in the later case than in the former case. The catecholase activity of the complexes reveals that the homobinuclear Cu(II) complexes show higher catalytic activity than the corresponding heterobinuclear Cu(II)-Zn(II) complexes. In the hydrolysis of 4-nitrophenylphosphate, the heterobinuclear Cu(II)-Zn(II) complexes show better catalytic activity than the corresponding homobinuclear Cu(II) complexes.
authors.affiliation: Department of Inorganic Chemistry, School of Chemical Sciences, University of Madras, Guindy Campus, Chennai 600 025, India.
authors.forename: K
authors.initials: K
authors.lastname: Shanmuga Bharathi
authors.forename: S
authors.initials: S
authors.lastname: Sreedaran
authors.forename: A
authors.initials: A
authors.lastname: Kalilur Rahiman
authors.forename: V
authors.initials: V
authors.lastname: Narayanan
mesh_terms: D004156:Catechol Oxidase / Q000378:metabolism; D002396:Catechols / Q000378:metabolism; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D055664:Electrochemical Techniques / Q000379:methods*; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D006868:Hydrolysis; D007700:Kinetics; D008280:Magnetics; D009596:Nitrophenols / Q000378:metabolism; D009943:Organophosphorus Compounds / Q000378:metabolism; D010084:Oxidation-Reduction; D017550:Spectroscopy, Fourier Transform Infrared; D013696:Temperature; D015032:Zinc / Q000737:chemistry*
chemical_list: D002396:Catechols; D056831:Coordination Complexes; D009596:Nitrophenols; D009943:Organophosphorus Compounds; C008644:nitrophenylphosphate; D003300:Copper; D004156:Catechol Oxidase; D015032:Zinc; C034221:catechol