Copper(II) complexes of tridentate selenobisphenolate ligand in mixed ligand environments: Synthesis, crystal structure, EPR and electrochemical studies

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Authors

MIJANUDDIN Md. RAY Ambarish MONDAL Parikshit Chandra MAREK Jaromír ALI Mahammad

Year of publication 2007
Type Article in Periodical
Magazine / Source Journal of Molecular Structure
MU Faculty or unit

Faculty of Science

Citation
Field Inorganic chemistry
Keywords copper(II) complexes; mixed ligand environment; square-pyramidal structures; cyclic voltammetric studies
Description A series of square-pyramidal copper(II) complexes, [Cu(L-Se)(N-N)] (H2LSe = seleno-bisphenolate; N-N = bipyridyl, phenanthroline or N,N-dimethylethylenediamine) have been synthesized and characterized by elemental analyses, magnetic measurements, IR, EPR, and electronic spectral studies. Single crystal X-ray structures of [Cu(L-Se)(bpy)]. H2O (2), [Cu(L-Se)(phen)]. CH2Cl2 (3) and [Cu(L-Se)(N,N-Me(2)en)] (4) showed that all the complexes have approximately square-pyramidal geometry. In complexes 2 and 3, the square plane is occupied by O(1) O(2) N(1) and N(2) and the apical position by Se atom of L(Se 2-)ligand. The asymmetric unit of complex 4 contains two crystallographically independent discrete molecules A and B with CuN2OSe chromophore comprising the square plane and the axial position being occupied by another phenolate oxygen atom. Complexes 2, 3 and 4 are found to be paramagnetic. Both the complexes 2 and 4 show three reduction processes: (a) a quasi-reversible reduction of Cu-II to Cu-I, (b) an irreversible reduction of Cu-I to Cu-0 with the release of free ligand, and (c) a reduction process occurs at this coordinated ligand. They also show a well-defined quasi-reversible oxidation of Cu-II to Cu-III and an irreversible oxidation peak at similar to 1.30 and 1.40 V vs. Ag/AgCl for 4 and 2, respectively, with no cathodic counterpart, and were attributed to the oxidation of the metal coordinated ligand. (c) 2006 Elsevier B.V. All rights reserved.
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