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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

Abstract:

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
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