Vanadium(IV,V) complexes of D-saccharic and mucic acids in aqueous solution

Dalton Transactions : an International Journal of Inorganic Chemistry
Agnes DörnyeiTamás Kiss

Abstract

The vanadium(IV,V) complexes formed with two aldaric acids (D-saccharic or D-glucaric acid, and mucic or galactaric acid) in aqueous solution were characterised by employing pH-potentiometry, EPR, multinuclear NMR and UV-VIS spectroscopy. The stoichiometry and stability constants of the complexes formed were determined at 25 degrees C and ionic strength I= 0.2 mol dm(-3)(KCl). The spectral measurements revealed that vanadium(IV,V) coordinates first at the terminal COO(-) functions, forming mononuclear complexes. At pH > 3, through the metal ion-induced deprotonation and coordination of the neighbouring alcoholic functions, (COO(-), O(-)) coordinated dinuclear complexes are formed, which predominate in the pH range 4-8. In the basic pH range, the ligand molecules are displaced and binary metal hydroxo and oxo complexes are present. EPR measurements at room temperature and at 140 K proved that formation of the VO(iv) dimers is more enhanced at room temperature, but at 140 K their dissociation is favoured. An interesting pH-dependent cis-trans isomeric equilibrium was assumed and analysed by EPR and molecular modelling in the case of the complexes [(VO)(2)L(2)H(x)](x=-2 and -4). Joint evaluation of the pH-potentiometric and (51)V ...Continue Reading

References

Dec 6, 1995·Molecular and Cellular Biochemistry·D C CransA D Keramidas
Jun 24, 2003·Inorganic Chemistry·Eugenio GarribbaDaniele Sanna
Mar 10, 2004·Chemistry : a European Journal·Andrea LakatosUNKNOWN Solution and Solid-State Study

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