Structural characterization and reactivity of γ-octamolybdate functionalized by proline

Abstract: The reaction of molybdate and dl-proline at pH 3.4 results in the formation of a Na4[Mo8O26(proO)2]·22H2O complex (pro=proline) in which two proline ligands are attached to molybdenum(VI) ions via monodentate coordination of the carboxylate groups. The structure of the complex was determined by single crystal X-ray diffraction and by combination of 1H, 13C and 95Mo NMR spectroscopy techniques in solution. The structure of the complex is strongly dependant on the pH. At native pH 3.4 the octamolybdate-type structure seems to be present in solution, but the increase of pH to 5.8 resulted in a rearrangement of the structure to a heptamolybdate-type structure. At physiological pH, the polyoxometalate framework was completely dissociated into the monomeric unit. The reactivity of the Na4[Mo8O26(proO)2]·22H2O towards the hydrolysis of ATP was tested at different pH values. While in solution at pH 3.4 the hydrolysis proceeded to yield AMP (adenosine monophosphate) and ADP (adenosine diphosphate) in nearly equal amounts, reaction mixture at pH 5.8 gave ADP as the only product of hydrolysis after 24h of reaction. At neutral pH, the hydrolysis of ATP was slower, but it proceeded to yield 75% of ADP after 48h of reaction. [Copyright &y& Elsevier]