An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides<sup>1</sup>

Diamond, R.M.; Street, Kenneth W.; Seaborg, Glenn T.

doi:10.1021/ja01635a001

Cited by 259 publications

(128 citation statements)

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“…[117][118][119] While lanthanides and actinides can exhibit significantly different chemical behaviors, the use of lanthanides as actinide analogs has enabled the advancement of actinide chemistry and continues to be useful. [120][121][122][123][124][125][126][127] For example, Ce 4+ and Pu 4+ have nearly identical ionic radii (0.87 and 0.86 Å, respectively) 128 and similar shifts in the 4+/3+ reduction potentials in aqueous solutions. 129 Figure 1.…”

Section: Introductionmentioning

confidence: 99%

A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹

et al. 2016

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Abstract.A tetravalent cerium macrocyclic complex (CeLK4) was prepared with an octadentate terephthalamide ligand comprised of hard catecholate donors, and characterized in the solution state by spectrophotometric titrations and electrochemistry, and in the crystal by X-ray diffraction. The solution state studies showed that L exhibits a remarkably high affinity towards Ce 4+ , with log β110 = 61(2) and ΔG = -348 kJ/mol, compared with log β110 = 32.02(2) for the analogous Pr 3+ complex. In addition, L exhibits an unusual preference for forming CeL 4-relative to formation of the analogous actinide complex, ThL 4-, which has β110 = 53.7(5). The extreme stabilization of tetravalent cerium relative to its trivalent state is also evidenced by the shift of 1.91 V in redox potential of the Ce 3+ /Ce 4+ couple of the complex (measured at -0.454 V vs. SHE). The unprecedented behavior prompted an electronic structure analysis using L3 and M5,4-edge X-ray absorption near-edge structure (XANES) spectroscopies and configuration interaction calculations, which showed that 4f orbital bonding in CeLK4 has partial covalent character owing to ligand-to-metal charge transfer (LMCT) in the ground state. The experimental results are presented in the context of earlier measurements on tetravalent cerium compounds, indicating that the amount LMCT for CeLK4 is similar to that observed for [Et4N]2[CeCl6] and CeO2, and significantly less than that for the organometallic sandwich compound cerocene, (C8H8)2Ce. A simple model to rationalize changes in 4f orbitals for tri-and tetravalent lanthanide and actinide compounds is also provided.

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Section: Introductionmentioning

confidence: 99%

A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹

et al. 2016

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“…Their slight differences in hardness (Pearson Hard and Soft Acid Base principle 1 ) make actinides more prone to develop covalent interactions with soft ligands, and thus provide an attractive solution for An/Ln separation. [2][3][4][5] Ligands bearing soft S, P and N atoms have been extensively studied (see for instance ref. [6][7][8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

DFT modeling of the relative affinity of nitrogen ligands for trivalent f elements: an energetic point of view

et al. 2007

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aIn many theoretical studies dealing with the selective complexation of trivalent actinides with respect to trivalent lanthanides, the method of calculation is assessed by comparing computed geometries with crystal structures that are often available. Yet, the selectivity is better rationalized through thermodynamic data, as enthalpy and entropy terms. In this article, we have theoretically modeled competing complexation reactions of [Ce(terpy) 3+ systems (terpy = 2,2 0 :6 0 2 00 -terpyridine; MeBTP = methyl-2,6-di(1,2,4-triazin-3-yl)pyridine) within the framework of the Density Functional Theory. Our calculations manage to qualitatively account for the experimental relative stabilities of terpy and MeBTP complexes, and in particular for the better coordinating strength of MeBTP for trivalent uranium. We also show by comparing the MeBTP ligand with its non-alkylated form (HBTP) that model systems often used in quantum chemistry must be carefully chosen when energetic comparisons are undertaken.

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“…At high ionic strength Np and Np are only slightly or not at all ad-4+ sorbed from HCl (143,438). From 9 N HCIO however, Np is strongly adsorbed (438).…”

Section: Inorganic Eluting Agentsmentioning

confidence: 94%

“…U '*' is strongly adsorbed from dilute HCl and the distribution coefficient decreases with increasing molarity (142,438). In 9 N HCl the distribution coefficient is less than 1.…”

Section: Inorganic Eluting Agentsmentioning

confidence: 98%

Cation-Exchange Techniques in Radiochemistry.

Massart¹

1971

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An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides¹

Cited by 259 publications

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A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹

A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹

DFT modeling of the relative affinity of nitrogen ligands for trivalent f elements: an energetic point of view

Cation-Exchange Techniques in Radiochemistry.

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An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides1

Cited by 259 publications

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A Macrocyclic Chelator That Selectively Binds Ln4+ over Ln3+ by a Factor of 1029

A Macrocyclic Chelator That Selectively Binds Ln4+ over Ln3+ by a Factor of 1029

DFT modeling of the relative affinity of nitrogen ligands for trivalent f elements: an energetic point of view

Cation-Exchange Techniques in Radiochemistry.

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An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides¹

A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹

A Macrocyclic Chelator That Selectively Binds Ln⁴⁺ over Ln³⁺ by a Factor of 10²⁹