Glutarimidedioxime: A Complexing, Reductive, and Nitrosyl Reagent for Molybdenum.

Glutarimidedioxime is a cyclic amidoxime moiety formed during the synthesis of amidoxime-functionalized fibers and apparently facilitates the extraction of uranium from seawater. Herein, we comprehensively explore differences between molybdenum and vanadium coordinated by glutarimidedioxime. The high adsorption of vanadium is explained by the formation of rare nonoxido vanadium(V) complexes, where each bare V is coordinated with two tridentate glutarimidedioxime ligands. By contrast, molybdenum is coordinated by only one glutarimidedioxime ligand, and the oxido Mo═O bonds in molybdate cannot be displaced by the ligand. Under seawater conditions, vanadium is fully complexed. Meanwhile, approximately 25% of molybdenum ions are in the form of free molybdate even if the concentration of glutarimidedioxime is 100000 times that of molybdenum. Glutarimidedioxime was expected to be more stable in the presence of metal ions than without them. However, complexation with molybdenum accelerated the degradation of the glutarimidedioxime ligand to release hydroxylamine. Molybdenum(VI) was then reduced by hydroxylamine, which itself was oxidized into nitrosyl. Vanadium heavily outcompetes adsorption of uranium, while molybdenum causes the degradation of glutarimidedioxime; the latter issue has previously been neglected and was first reported here.