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Coordination Features of a Polyaza-Bipyridine-Macrocyclic Ligand toward Co(II) and Cd(II) in Water and Dimethylsulfoxide

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Abstract

The coordination features of a polyaza macrocycle, containing the diverse bipyridine unit 4,4′-(2,5,6,11,14-pentaaza[15]-[15](2,2′)-bipyridylophane (L3), with Co(II) and Cd(II) have been studied in aqueous solution and in the aprotic solvent dimethylsulfoxide (DMSO). The study was carried out at 298 K by means of potentiometric, spectrophotometric and calorimetric techniques. The formation of the dinuclear species M2 L3 is observed for Co(II) both in water and in DMSO, whereas Cd(II) is able to form this type of dinuclear complex only in DMSO. The FT-IR spectra of the mononuclear species ML3, formed in both solvents, provide evidence that the rigid structure of the polyaminic chain prevents metal ions from being coordinated by all of the nitrogens of the macrocyclic cavity, in good agreement with the behavior suggested by the thermodynamic parameters. The results are compared with those for the complexation of Co(II) and Cd(II) with similar polyazamacrocycles containing a bipyridine unit directly inside the cavity. Semi-empirical calculations were also performed to obtain structural information.

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Authors and Affiliations

  1. Dipartimento di Chimica, Polo Scientifico, Università di Firenze, Via della Lastruccia 3, 50019, Sesto Fiorentino, Italy

    Andrea Bencini, Antonio Bianchi, Claudia Giorgi & Barbara Valtancoli

  2. Dipartimento di Scienze e Tecnologie Chimiche, Università di Udine, Via Cotonificio 108, 33100, Udine, Italy

    Silvia Del Piero, Andrea Melchior, Roberto Portanova & Marilena Tolazzi

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  1. Andrea Bencini
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  2. Antonio Bianchi
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  3. Silvia Del Piero
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  4. Claudia Giorgi
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  8. Barbara Valtancoli
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Correspondence to Andrea Bencini.

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Bencini, A., Bianchi, A., Del Piero, S. et al. Coordination Features of a Polyaza-Bipyridine-Macrocyclic Ligand toward Co(II) and Cd(II) in Water and Dimethylsulfoxide. J Solution Chem 37, 503–517 (2008). https://doi.org/10.1007/s10953-008-9249-3

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