Synthesis and physiochemical studies on binuclear Cu(II) complexes derived from 2,6-[(N-phenylpiperazin-1-yl)methyl]-4-substituted phenols |
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| Authors: | S Karthikeyan T M Rajendiran R Kannappan R Mahalakshmy R Venkatesan and P Sambasiva Rao |
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| Institution: | (1) Department of Chemistry, Pondicherry University, RV Nagar, Kalapet, 605 014 Pondicherry, India |
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| Abstract: | Preparation of the ligands HL1 = 2,6-(N-phenylpiperazin-1-yl)methyl]-p-ethylphenol; HL2 = 2,6-(N-phenylpiperazin-1-yl)methyl]-p-methoxyphenol and HL3 = 2,6-(N-phenylpiperazin-1-yl)methyl]-p-nitrophenol are described together with their Cu(II) complexes with different bridging units. The exogenous bridges incorporated
into the complexes are: hydroxo Cu2L(OH)(H2O)2](ClO4)2.H2O (L1=1a, L2 =1b, L3 =1c), acetato Cu2L(OAc)2]ClO4.H2O (L1 =2a, L2 =2b, L3 =2c) and nitrito Cu2L1(NO2)2(H2O)2]ClO4.H2O (L1=3a, L2 =3b, L3 =3c). Complexes1a,1b,1c and2a,2b,2c contain bridging exogenous groups, while3a,3b,3c possess only open μ-phenolate structures. Both the ligands and complexes were characterized by spectral studies. Cyclic voltammetric
investigation of these complexes revealed that the reaction process involves two successive quasireversible one-electron steps
at different potentials. The first reduction potential is sensitive to electronic effects of the substituents at the aromatic
ring of the ligand system, shifting to positive potentials when the substituents are replaced by more electrophilic groups.
EPR studies indicate very weak interaction between the two copper atoms. Various covalency parameters have been calculated. |
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| Keywords: | Unsymmetrical ligands dinuclear complexes synthetic models cyclic voltammetry |
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