Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants

Drew, Michael G. B.; Foreman, Mark; Geist, Andreas; Hudson, Michael J.; Marken, Frank; Norman, Virginia; Weigl, Michael

doi:10.1016/j.poly.2005.09.030

Cited by 47 publications

(23 citation statements)

References 36 publications

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“…Predictably, [Ru(L)Cl 2 (CO)] where L is a pincer with pyrazines, C 4 N 2 rings, at both arms (A in Scheme ), has a lower CO stretching frequency, 1978 cm – 1 , and is more difficult to reduce than the btzp analog; thus selective ring choice permits tuning of the electronic structure of any such pincer complex . Incremental changes towards increasing ease of reduction (based on E 1/2 value, vs. A) are likewise seen with the more heavily nitrogen‐loaded 1,2,4‐triazin‐3‐yl armed pincer (B) complexes of 3d metals . A bis ( 1,2,4‐triazin‐3‐yl) pyridine complex of ruthenium(II) has been investigated for transfer hydrogenation catalysis, but its electronic characteristics have not been studied …”

Section: Discussionmentioning

confidence: 99%

Gauging the Redox Non‐Innocence of a Highly Pi‐Acidic Bis‐Tetrazine Pincer Ligand

et al. 2019

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A 1:1 complex of a 2,6-bis-tetrazinylpyridine pincer ligand, btzp, with ZnCl 2 is characterized. The molecule is shown to be redox active by cyclic voltammetry and by chemical reduction. The resulting monoanion loses chloride to yield a radical species [Zn(btzp)Cl] whose EPR spectrum is observed. DFT studies show that the electron added upon reduction goes into an orbital primarily comprised of tetrazine nitrogen pπ character. The Zn-Cl bonds lengthen but the Zn-N tz bonds shorten upon reduction, in response to taking on amide character. In [a]

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Section: Discussionmentioning

confidence: 99%

Gauging the Redox Non‐Innocence of a Highly Pi‐Acidic Bis‐Tetrazine Pincer Ligand

et al. 2019

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“…Drew et al described the formation of homoleptic complexes of some BTP ligands with first-row transition metals. [28] They found that Co, Ni, Pd, Cd, Pb, Zr, and Ru nitrosyl were well extracted by some BTP ligands. They also isolated several crystals from BTP complexes with Mn, Fe, Co, and Zn.…”

Section: Extraction From Simulated Har Solutionmentioning

confidence: 99%

Direct Selective Extraction of Actinides (III) from PUREX Raffinate using a Mixture of CyMe₄BTBP and TODGA as 1-cycle SANEX Solvent

Wilden

Schreinemachers

Sypuła

et al. 2011

Solvent Extraction and Ion Exchange

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Within the framework of our research activities related to the partitioning of spent nuclear-fuel solutions, the direct selective extraction of trivalent actinides from a simulated PUREX raffinate was studied using a mixture of CyMe 4 BTBP and TODGA (1-cycle SANEX). The solvent showed a high selectivity for trivalent actinides with a high lanthanide separation factor. However, the coextraction of some fission product elements (Cu, Ni, Zr, Mo, Pd, Ag, and Cd) from a simulated PUREX raffinate was observed, with distribution ratios up to 30 (Cu). The extraction of Zr and Mo could be suppressed using oxalic acid but the use of the well-known Pd complexant N-(2-Hydroxyethyl)-ethylendiamin-N,N ,N -triacetic acid (HEDTA) was unsuccessful. During screening experiments with different amino acids and derivatives, the sulfur-bearing amino acid L-Cysteine showed good complexation of Pd and prevented its extraction into the organic phase without influencing the extraction of the trivalent actinides Am (III) and Cm (III). The optimization studies included the influence of the L-Cysteine and HNO 3 concentration and the kinetics of the extraction. The development of a process-like extraction series showed very promising results in view of further optimizing the process. A strategy for a single-cycle process is proposed within this article.

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“…Using BTP 69 and hemi-BTP 94, many of these metals were extracted into the organic phase with D values in some cases higher than those observed for Am(III). 91 This is significant because these metals in high enough concentrations could disrupt an Am(III) extraction process by sequestering the extractant. A number of homoleptic octahedral complexes of the hemi-BTPs with manganese(II), iron(II), cobalt(II), and zinc(II) were also characterized by X-ray crystallography.…”

Section: 4-triazin-3-yl)pyridine (Btp) and Related Ligandsmentioning

confidence: 99%

Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

Lewis¹,

Hudson²,

Harwood³

2011

Synlett

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This account summarizes recent work by us and others on the development of ligands for the separation of actinides from lanthanides contained in nuclear waste streams in the context of a future European strategy for nuclear waste management. The current status of actinide/lanthanide separations worldwide is briefly discussed, and the synthesis, development, and testing of different classes of heterocyclic soft N-and S-donor ligands in Europe over the last 20 years is presented. This work has led to the current benchmark ligand that displays many of the desirable qualities for industrial use. The improvement of radiolytic stability through ligand design is also discussed.

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Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants

Cited by 47 publications

References 36 publications

Gauging the Redox Non‐Innocence of a Highly Pi‐Acidic Bis‐Tetrazine Pincer Ligand

Gauging the Redox Non‐Innocence of a Highly Pi‐Acidic Bis‐Tetrazine Pincer Ligand

Direct Selective Extraction of Actinides (III) from PUREX Raffinate using a Mixture of CyMe₄BTBP and TODGA as 1-cycle SANEX Solvent

Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

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Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants

Cited by 47 publications

References 36 publications

Gauging the Redox Non‐Innocence of a Highly Pi‐Acidic Bis‐Tetrazine Pincer Ligand

Gauging the Redox Non‐Innocence of a Highly Pi‐Acidic Bis‐Tetrazine Pincer Ligand

Direct Selective Extraction of Actinides (III) from PUREX Raffinate using a Mixture of CyMe4BTBP and TODGA as 1-cycle SANEX Solvent

Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle

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Direct Selective Extraction of Actinides (III) from PUREX Raffinate using a Mixture of CyMe₄BTBP and TODGA as 1-cycle SANEX Solvent