Abstract
The reaction of Schiff bases formed in reaction of 2-(aminomethyl)pyridine and aliphatic ketones (acetone, dihexyl ketone, 2- and 4-heptanone) or 2-acetylpyridine and 2-aminoethanol with K3Na[Mo(CN)4O2]·6H2O in water–ethanol solution results in isolation of two new complexes of formulae: (PPh4)[Mo(CN)3O(ampy)]·2H2O (1) (ampy=2-(aminomethyl)pyridine) and (PPh4)[Mo(CN)3O(aceamet)]·2H2O (2) (aceamet=2-{[1-(pyridin-2-yl)ethyl]amino}ethanol). The isolated salts were characterized by elemental analysis, single crystal X-ray structure measurements, IR and UV–Vis spectroscopy and cyclic voltammetry. The complexes crystalize in monoclinic (1) or triclinic (2) space group with very distorted geometry of the anion with almost identical MoO distance (1.674 and 1.673Å for 1 and 2, respectively). The energy of intense MLCT transitions in visible part of the spectra were found to be dependent on pyridine ring position (cis in 1 and trans in 2) to MoO bond and show strong solvatochromic effect dependent on the nature of the solvent. The very unusual position of pyridine ring in 2 as well as coordination of only 2-(aminomethyl)pyridine in 1 is discussed in terms of the reaction scheme in which for both salts only Schiff base ligand components [chelating 2-(aminomethyl)pyridine or 2-acetylpyridine] are coordinated at first reaction step. The results presented in paper indicate, that the Schiff bases cannot be treated as typical stable organic ligands, but rather as a complex system. The metal (or complex) determine which element of this system and in what sequence is coordinated.
Published Version
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