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Journal of Coordination Chemistry
Year: 2009  |  Volume: 62  |  Issue: 5  |  Page No.: 734 - 744

Synthesis, crystal structure, and electrochemistry of [Co{(Me-sal)2dien}(N3)] and [Co{(Me-sal)2dpt}(N3)]

Soraia Meghdadi, Kurt Mereiter, Mehdi Amirnasr, Farzaneh Fadaee and Ahmad Amiri    

Abstract: The structure, spectroscopic, and electrochemical properties of [Co{(Me-sal)2dien}(N3)] and [Co{(Me-sal)2dpt}(N3)], where (Me-sal)2dien = 2,2`-[1,1`-(3-azapentane-1,5-diyldinitrilo)diethylidyne] diphenolate and (Me-sal)2dpt = 2,2`-[1,1`-(4-azapentane-1,7-diyldinitrilo)diethylidyne] diphenolate, have been investigated. These complexes have been characterized by elemental analyses, IR, UV-Vis, and 1H-NMR spectroscopy. The crystal structures of these complexes have been determined by X-ray diffraction. Complex 1 crystallizes in the triclinic space group P1, with a = 7.8443(4) , b = 11.0660(5) , c = 11.6216(6) , α = 73.360(1)°, β = 76.965(1)°, γ = 84.436(1)° and Z = 2. Complex 2 crystallizes in the monoclinic space group P21/n, with a = 12.1985(13) , b = 10.9332(12) , c = 15.2808(16) , β = 76.965(1)° and Z = 4. The coordination geometry around cobalt(III) in both complexes is a distorted octahedron. The electrochemical reduction of these complexes at a glassy carbon electrode in acetonitrile indicates that the first reduction corresponding to CoIII-CoII is electrochemically irreversible, accompanied by dissociation of the axial Co-N(N3) bond. The second reduction step of Co(II/I) leads to decomposition of the complex. These observations are rationalized based on the structure-function relations.

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