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Issue 12, 2004
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Bis- and tris-(methylphosphonic) acid derivatives of a 14-membered tetraazamacrocycle containing pyridine: synthesis, protonation and complexation studies

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Abstract

Two N-methylphosphonic acid derivatives of a 14-membered tetraazamacrocycle containing pyridine have been synthesized, H4L1 and H6L2. The protonation constants of these compounds and the stability constants of complexes of both ligands with Ni2+, Cu2+ and Zn2+ were determined by potentiometric methods at 298 K and ionic strength 0.10 mol dm−3 in NMe4NO3. The high overall basicity of both compounds is ascribed to the presence of the phosphonate arms. 1H and 31P NMR spectroscopic titrations were performed to elucidate the sequence of protonation, which were complemented by conformational analysis studies. The complexes of these ligands have stability constants of the order of or higher than those formed with ligands having the same macrocyclic backbone but acetate arms. At pH = 7 the highest pM values were found for solutions containing the compound with three acetate groups, followed immediately by those of H6L2, however, as expected, the increasing pH favours the complexes of ligands containing phosphonate groups. The single-crystal structure of Na2[Cu(HL1)]NO3·8H2O has shown that the coordination geometry around the copper atom is a distorted square pyramid. Three nitrogen atoms of the macrocyclic backbone and one oxygen atom from one methylphosphonate arm define the basal plane, and the apical coordination is accomplished via the nitrogen atom trans to the pyridine ring of the macrocycle. To achieve this geometric arrangement, the macrocycle adopts a folded conformation. This structure seems consistent with Uv-vis-NIR spectroscopy for the Ni2+ and the Cu2+ complexes and with the EPR for the latter.

Graphical abstract: Bis- and tris-(methylphosphonic) acid derivatives of a 14-membered tetraazamacrocycle containing pyridine: synthesis, protonation and complexation studies

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Publication details

The article was received on 16 Mar 2004, accepted on 26 Apr 2004 and first published on 10 May 2004


Article type: Paper
DOI: 10.1039/B403977G
Citation: Dalton Trans., 2004,0, 1812-1822
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    Bis- and tris-(methylphosphonic) acid derivatives of a 14-membered tetraazamacrocycle containing pyridine: synthesis, protonation and complexation studies

    K. P. Guerra, R. Delgado, L. M. P. Lima, M. G. B. Drew and V. Félix, Dalton Trans., 2004, 0, 1812
    DOI: 10.1039/B403977G

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