Experimental evidence for a second coordination sphere water molecule in the hydration structure of YbDTPA - Insights for a re-assessment of the relaxivity data of GdDTPA

The low temperature (-100 °C) X-ray structure of the complex K₂[Yb(DTPA)(H₂O)] has been determined. The metal ion is at the center of a tricapped trigonal prism and is nine-coordinate, binding to the three nitrogens and five oxygens of the ligand and one water molecule. From the structure obtained, three well-defined hydration shells can be observed consisting of: i) one coordinated water molecule; ii) several water molecules in the outer coordination sphere of the Yb(III) ion and iii) one water molecule surprisingly close to the metal center and hydrogen-bonded to proximate carboxylate groups. A variable-field and temperature NMRD study of the corresponding Gd complex has been performed and the data interpreted by taking into account the presence of second-sphere water molecule(s). The results of the analysis are in excellent agreement with the X-ray structural data.