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Issue 9, 2004
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Mixed nitrogen/oxygen ligand affinities for bipositive metal ions and dioxygen binding to cobalt(II) complexes

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Abstract

The complex formation of Co(II) and Cd(II) with mixed N/O ligands in dimethylsulfoxide (dmso) at 298 K is investigated by means of potentiometric, UV-Vis, calorimetric, FT-IR, NMR and electrochemical techniques. The linear and cyclic ligands investigated are: 2,2′-oxydiethylamine (NON), N-(2-hydroxyethyl)-ethylenediamine (NNO), 1,4,10-trioxa-7,13-diaza-cyclopentadecane (2,1) and 1,4,7,10-tetraoxa-13-azacyclopentadecane (2,2). The results are discussed by taking into account the donor strength of donor atoms, strain effects in the formation of chelate rings, steric and inductive effects and the size of the cavity when macrocyclic ligands are concerned. DFT studies are also performed to gain an insight into the stabilization of the lower oxidation state of the CoL22+/3+ couple in order to understand the different reactivity of the Co(II) complexes towards dioxygen. The kinetics of dioxygen uptake has been studied by UV-Vis measurements and the results reveal an interesting strong solvent effect, which is active in lowering the rate constant for formation of the initial superoxo complex.

Graphical abstract: Mixed nitrogen/oxygen ligand affinities for bipositive metal ions and dioxygen binding to cobalt(ii) complexes

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Publication details

The article was received on 17 Feb 2004, accepted on 12 Mar 2004 and first published on 02 Apr 2004


Article type: Paper
DOI: 10.1039/B402394C
Citation: Dalton Trans., 2004,0, 1358-1365
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    Mixed nitrogen/oxygen ligand affinities for bipositive metal ions and dioxygen binding to cobalt(II) complexes

    S. Del Piero, A. Melchior, P. Polese, R. Portanova and M. Tolazzi, Dalton Trans., 2004, 0, 1358
    DOI: 10.1039/B402394C

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