Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution.

Autor: Leggett CJ; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov., Parker BF; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov.; Department of Chemistry , University of California - Berkeley , Berkeley , CA 94720 , USA., Teat SJ; Advanced Light Source , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: SJTeat@lbl.gov., Zhang Z; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov., Dau PD; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov., Lukens WW; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov., Peterson SM; National Security Directorate , Pacific Northwest National Laboratory , 902 Battelle Blvd. , Richland , WA 99352 , USA., Cardenas AJP; Fundamental and Computational Sciences Directorate , Pacific Northwest National Laboratory , 902 Battelle Blvd. , Richland , WA 99352 , USA., Warner MG; National Security Directorate , Pacific Northwest National Laboratory , 902 Battelle Blvd. , Richland , WA 99352 , USA., Gibson JK; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov., Arnold J; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov.; Department of Chemistry , University of California - Berkeley , Berkeley , CA 94720 , USA., Rao L; Chemical Sciences Division , Lawrence Berkeley National Laboratory , 1 Cyclotron Road , Berkeley , CA 94720 , USA . Email: LRao@lbl.gov.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2016 Apr 01; Vol. 7 (4), pp. 2775-2786. Date of Electronic Publication: 2016 Jan 14.
DOI: 10.1039/c5sc03958d
Abstrakt: A non-oxido V(v) complex with glutaroimide-dioxime (H 3 L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L) 2 ]·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 (L 3- ) coordinating to V 5+ , each in a tridentate mode via the imide N ( R V-N = 1.96 Å) and oxime O atoms ( R V-O = 1.87-1.90 Å). Using 17 O-labelled vanadate as the starting material, concurrent 17 O/ 51 V/ 1 H/ 13 C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V[double bond, length as m-dash]O bonds by glutaroimide-dioxime and verified the existence of the "bare" V 5+ /glutaroimide-dioxime complex, [V(L) 2 ] - , in aqueous solution. In addition, the crystal structure of an intermediate 1 : 1 V(v)/glutaroimide-dioxime complex, [VO 2 (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 V 5+ complexes and the unprecedented demonstration of the displacement of the oxido V[double bond, length as m-dash]O bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications.
(This journal is © The Royal Society of Chemistry 2016.)
Databáze: MEDLINE
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