Complexation of U(VI) with diphenyldithiophosphinic acid: spectroscopy, structure and DFT calculations

Meng, Dechao; Pu, Ning; Mei, Lei; Sun, Taoxiang; Xu, Lei; Shi, Wei‐Qun; Chen, Jing; Xu, Chao

doi:10.1007/s10967-018-5844-y

Cited by 1 publication

(3 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this work, we successfully synthesized single crystals of UO 2 2+ with the two S 2 PR 2 À ligands. The crystal structures of the UO 2 (S 2 PR 2 ) 2 (EtOH) complexes are shown in , similar to previous reports (Meng et al, 2018;Pinkerton et al, 1997;Storey et al, 1983). Both the two UO 2 (S 2 PR 2 ) 2 (EtOH) complexes contain four sulfur atoms from the two bidentate dithiophosphinate ligands and one oxygen atom from the coordinated ethanol in the first coordinated sphere of the equatorial plane of UO 2…”

Section: Complexes Of Uosupporting

confidence: 83%

“…UO 2 (S 2 PPh 2 ) 2 (EtOH). Single crystals of the UO 2 (S 2 PR 2 ) 2 (EtOH) complexes were prepared using the reported procedures with slight modifications (Meng et al, 2018;Pinkerton et al, 1997;Storey et al, 1983). A solution of [NH 4 ][S 2 PPh 2 ] (54.2 mg, 0.203 mmol) in ethanol (2 ml) was mixed with a solution of UO 2 Cl 2 (35.8 mg) in ethanol (2 ml).…”

Section: Methodsmentioning

confidence: 99%

“…2+ with S 2 PR 2 À (R = Ph, o-CF 3 C 6 H 4 ) ligands were prepared and isolated as highly pure crystalline solids before the XAS experiments. Note that the complexes of UO 2 2+ with the S 2 PPh 2 À ligand have been crystalized previously (Meng et al, 2018;Pinkerton et al, 1997;Storey et al, 1983). However, the crystal structures of the complexes of UO 2 2+ with the S 2 P(o-CF 3 C 6 H 4 ) 2 À ligand have not been reported.…”

Section: Complexes Of Uomentioning

confidence: 99%

See 2 more Smart Citations

Covalency between the uranyl ion and dithiophosphinate by sulfur K-edge X-ray absorption spectroscopy and density functional theory

Zhang¹,

Duan²,

Wang³

et al. 2022

J Synchrotron Radiat

Self Cite

View full text Add to dashboard Cite

The dithiophosphinic acids (HS2PR 2) have been used for the selective separation of trivalent actinides (AnIII) from lanthanides (LnIII) over the past decades. The substituents on the dithiophosphinic acids dramatically impact the separation performance, but the mechanism is still open for debate. In this work, two dithiophosphinic acids with significantly different AnIII/LnIII separation performance, i.e. diphenyl dithiophosphinic acid (HS2PPh2) and bis(ortho-trifluoromethylphenyl) dithiophosphinic acid [HS2P(o-CF3C6H4)2], are employed to understand the substituent effect on the bonding covalency between the S2PR 2 − anions (R = Ph and o-CF3C6H4) and the uranyl ion by sulfur K-edge X-ray absorption spectroscopy (XAS) in combination with density functional theory calculations. The two UO2(S2PR 2)(EtOH) complexes display similar XAS spectra, in which the first pre-edge feature with an intensity of 0.16 is entirely attributed to the transitions from S 1s orbitals to the unoccupied molecular orbitals due to the mixing between U 5f and S 3p orbitals. The Mulliken population analysis indicates that the amount of \% S 3p character in these orbitals is essentially identical for the UO2(S2PPh2)2(EtOH) and UO2[S2P(o-CF3C6H4)2]2(EtOH) complexes, which is lower than that in the U 6d-based orbitals. The essentially identical covalency in U—S bonds for the two UO2(S2PR 2)2(EtOH) complexes are contradictory to the significantly different AnIII/LnIII separation performance of the two dithiophosphinic acids, thus the covalency seems to be unable to account for substituent effects in the AnIII/LnIII separation by the dithiophosphinic acids. The results in this work provide valuable insight into the understanding of the mechanism in the AnIII/LnIII separation by the dithiophosphinic acids.

show abstract

Section: Complexes Of Uosupporting

confidence: 83%

Section: Methodsmentioning

confidence: 99%