期刊
CHEMICAL SCIENCE
卷 7, 期 4, 页码 2775-2786出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc03958d
关键词
-
资金
- Fuel Cycle Research and Development Campaign (FCRD)/Fuel Resources Program, Office of Nuclear Energy, the U.S. Department of Energy (USDOE), at Lawrence Berkeley National Laboratory (LBNL)
- Nuclear Energy University Program (NEUP) at University of California, Berkeley (UCB)
- USDOE, Office of Science, Office of Basic Energy Sciences
- USDOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Biosciences, and Geosciences Division (CSGB), Heavy Element Chemistry Program at LBNL [DE-AC02-05CH11231]
- FCRD/Fuel Resources Program, Office of Nuclear Energy, USDOE, at Pacific Northwest National Laboratory (PNNL)
A non-oxido V(V) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)(2)]center dot 2H(2)O, and the structure determined by X-ray diffraction. It is the first non-oxido V(V) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3-) coordinating to V5+, each in a tridentate mode via the imide N (RV-N = 1.96 angstrom) and oxime O atoms (RV-O = 1.87-1.90 angstrom). Using O-17-labelled vanadate as the starting material, concurrent O-17/V-51/H-1/C-13 NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V=O bonds by glutaroimide-dioxime and verified the existence of the bare V5+/glutaroimide-dioxime complex, [V(L)(2)](-), in aqueous solution. In addition, the crystal structure of an intermediate 1 : 1 V(V)/glutaroimide-dioxime complex, [VO2(HL)](-), in which the oxido bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS. Results from this work provide important insights into the strong sorption of vanadium on poly(amidoxime) sorbents in the recovery of uranium from seawater. Also, because vanadium plays important roles in biological systems, the syntheses of the oxido and non-oxido V5+ complexes and the unprecedented demonstration of the displacement of the oxido V=O bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications.
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