Dinuclear copper complexes with cyanamide derivatives as bridging ligands |
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| Authors: | Hassan Hadadzadeh Ali R Rezvani Hadi Esfandiari |
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| Institution: | 1. Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran;2. Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan, Iran |
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| Abstract: | Three mixed-valence copper complexes {Cu(phen)2}2(μ-L)](PF6)2 (where phen = 1,10-phenanthroline, L = 1,4-dicyanamidobenzene (dicyd)), 1,4-dicyanamido-2,5-dimethylbenzene (Me2dicyd) and 1,4-dicyanamido-2,5-dichlorobenzene (Cl2dicyd), and one dinuclear Cu(II) complex {Cu(phen)2}2(μ-apc)](PF6)3 (where apc = monoanion of 4-azo(phenylcyanamido)benzene) have been prepared and characterized by elemental analysis, IR and electronic absorption spectroscopies and cyclic voltammetry. {Cu(phen)2}2(μ-apc)](PF6)3 · 2CH3COCH3 crystallized in the triclinic system and both five-coordinate Cu(II) ions in the dinuclear unit are linked through a bridging 4-azo(phenylcyanamido)benzene (apc) ligand. The cyanamide group (NCN) of the bridging ligand is coordinated to Cu(II) ions through the cyano-nitrogen and amido-nitrogen. The bond length between Cu(1) and cyano-nitrogen is slightly larger than that formed by Cu(2) and amido-nitrogen. The angular structural index parameters, τ, for Cu(1) and Cu(2) are 0.9 and 0.5, respectively. The copper(II) atoms display a different geometry with a N5 chromophore group. The intra Cu?Cu separation is 5.156(1) Å. All of the dicyd dinuclear copper complexes show radical anion absorption. |
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| Keywords: | Mixed-valence copper complex Radical anion absorption Cyclic voltammetry 1 4-Dicyanamidobenzene derivatives Crystal structure |
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