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Synthesis and Platinum (II) Complexes of Different Polyazacyclophane Receptors
* 1 , 1 , 1 , 2 , 3 , 1
1  Instituto de Ciencia Molecular, Departamento de Química Inorgánica, Universidad de Valencia, Spain
2  Innotecno Development SL, Parc Científic, Paterna, Valencia, Spain
3  Departament de Química Física, Universitat de València, Spain


During the last years, research on coordination chemistry of platinum has aroused great interest due to their potential biological applications. Herein, we report the interaction of PtCI42- with different polyazacyclophanes containing a pyridine unit as aromatic spacer. Formation of complexes has been studied by 1H and 195Pt NMR spectroscopy. Analysis of the recorded spectra of D2O solutions containing L and PtCl42- in a 1:1 molar ratio at acidic pH shows the evolution with time of the 1H and 195Pt signals. Different crystal structures have been solved by X-ray diffraction analysis. At acidic pHs, the metal ion is coordinated by the central amino group of the macrocyclic cavity and three chloride or bromide atoms, in a square planar geometry. Formation of [Pt(H2L1)Br3]Br (1) and [Pt(H2L2)Br3]Br (2) reveals the rapid substitution of chloride ligands in PtCl42- by bromide ligands. However, as reveals the crystal structure obtained for [PtIVL3Br2](PtBr4)(H2O) (4), at slightly higher pH values, the metal ion is coordinated through all nitrogen atoms of the macrocyclic cavity and an oxidation to Pt(IV) occurs.

Keywords: platinum, polyazacyclophane, coordination chemistry