A “directed” approach toward a cationic molecular square containing four isonicotinamidate ligands and (4 + 2) (en)Pt metal entities |
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Authors: | Anzhela Galstyan Bernhard Lippert |
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Affiliation: | a Fakultät Chemie, Technische Universität Dortmund, 44221 Dortmund, Germany b Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza - CSIC, 50009 Zaragoza, Spain |
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Abstract: | The use of 4-cyanopyridine (4-CNpy) and 3-cyanopyridine (3-CNpy) as ditopic ligands with 180° and 120° directionalities, respectively, for the construction of molecular architectures with the 90° metal fragments (en)PtII and (en)PdII in water is hampered by the ease with which these ligands undergo hydrolysis to isonicotinamide (4-C(O)NH2py) and nicotinamide (3-C(O)NH2py). As described in this article, out of six X-ray structurally characterized complexes (1-6), only a single one (1) reveal coordination of the unchanged ligand (4-CNpy) to (en)PtII. Nevertheless also the hydrolysis products are of interest in the context of obtaining discrete metallacyclic compounds: Thus, (en)PtII and 4-C(O)NH2py form a hexanuclear complex, [PF6⊂{(en)Pt}6(4-C(O)NHpy)4](NO3)7·10H2O (2), in which the anionic isonicotinamidate ligands function as tridentate, bridging ligands to produce a hybrid between a metallasquare and a 2-floor open box. The resulting cation with a +8 charge accommodates a single hexafluorophosphate anion in its interior. Adjacent cations of 2 pack in such a way as to develop Pt4 chains as typically seen in “platinum blues” and their [PtII]4 precursors. |
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Keywords: | 4-Cyanopyridine 3-Cyanopyridine Nitrile hydrolysis Molecular square Platinum Palladium |
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