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  • Title: Spectroscopic and theoretical studies on axial coordination of bis(pyrrol-2-ylmethyleneamine)phenyl complexes.
    Author: Chen JM, Ruan WJ, Meng L, Gao F, Zhu ZA.
    Journal: Spectrochim Acta A Mol Biomol Spectrosc; 2008 Nov 01; 71(1):191-8. PubMed ID: 18243780.
    Abstract:
    Metal (M = Zn(II), Ni(II), Cu(II)) complexes with tetradentate Schiff base ligand, bis(pyrrol-2-ylmethyleneamine)phenyl, has been synthesized and characterized by elemental analyses, 1H NMR, mass spectra and UV-vis spectra. The standard association constants (Ktheta) and the thermodynamic parameters (Delta(r)Hmtheta,Delta(r)Smtheta,Delta(r)Gmtheta) for axial coordination of imidazole derivatives with these Shiff base complexes were measured with UV-vis spectrophotometric titration. The decrease of enthalpy is found to be the drive of the axial coordination. Our Schiff base complexes can incorporate two axial ligands, except 2-Et-4-MeIm with two big substituents of great steric bulk according to stoichiometry of 1:1. ZnL displays high selectively binding to imidazole due to the steric bulk effect. Supporting density functional theory (DFT) calculations have been undertaken on B3LYP/6-31G(d) level.
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