High Yield, One-Pot Syntheses of Symmetrical Diaryl-N,N-Dialkyl Carbamoylmethylphosphine Oxide (CMPO) Ligands

Guillory, Paulette; Kapoor, Rupam; Pannell, Keith H.; Schulte, Louis D.; McKee, Steven D.; Zhang, Zhi Yi; Bartsch, Richard

doi:10.1081/scc-120015718

Cited by 4 publications

(7 citation statements)

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“…These resins contained only two peaks at the time of fabrication. 41 For m-CMPO DAAP , δ25.9 ppm (m-CMPO) and δ31.9 ppm (DAAP) peaks were observed. For m-CMPO TBP , δ25.9 ppm (m-CMPO) and δ-0.78 ppm (TBP) peaks were observed.…”

Section: ■ Results and Discussionmentioning

confidence: 93%

“…For m- CMPO DAAP and m- CMPO TBP , the spectra were more complicated. These resins contained only two peaks at the time of fabrication . For m -CMPO DAAP , δ25.9 ppm ( m- CMPO) and δ31.9 ppm (DAAP) peaks were observed.…”

Section: Resultsmentioning

confidence: 99%

“…Adsorption of the m- CMPO extractant and phase transfer catalysts (TBP and DAAP) to resin beads was achieved using a LANL procedure reported previously by McKee et al (Figure ). , Many aspects of the fabrication procedure are attractive. This resin preparation proceeded in near-quantitative yield.…”

Section: Resultsmentioning

confidence: 99%

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Characterizing Extraction Chromatography for Large-Scale Americium-241 Processing

Arko

Dan

Adelman

et al. 2021

Ind. Eng. Chem. Res.

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The americium-241 ( 241 Am) radioisotope has valuable nuclear properties that find broad industrial usage. Ensuring stable supplies of 241 Am is critical for supporting (and expanding) the existing 241 Am-application space and enabling emerging 241 Amtechnologies that are important for economic growth, energy, and national security. Unfortunately, the United States halted 241 Am production in 1984 and the existing inventory was depleted in the early 2000s. This situation recently changed when the U.S. Department of Energy Isotope Program established 241 Am recovery at Los Alamos National Laboratory. Today, large-scale quantities of 241 Am are now obtained using the Chloride Extraction and Actinide Recovery (CLEAR) process. This method uses a resin that has the di-(4-t-butylphenyl)-N,N-di-iso-butylcarbamoylmethylphosphine oxide (m-CMPO) extractant adsorbed on a resin bead to harvest 241 Am from plutonium-containing waste streams. To maintain and improve CLEAR processing of 241 Am, we have evaluated the extraction of 241 Am by m-CMPO as a function of three important processing relevant variables: (1) HCl concentration, (2) metal contaminant concentration, and (3) contact time. The performance of the m-CMPO resin was additionally compared against commercially available resins, namely, rare earth (RE) resin and a selected series of diglycolamide (DGA) resins. Our results suggested that the m-CMPO resin outperformed most of the commercially available alternatives. However, tetraoctyl-DGA (TODGA) and tetraethyl-hexyl-DGA (TEHDGA) prevailed on several fronts. The TODGA and TEHDGA resins quantitatively released 241 Am at low HCl concentrations (<0.5 M), were less susceptible to deleterious side effects from metal contaminants in the mobile phase and bound 241 Am faster. Based on these results, we concluded that 241 Am recovery yields have the potential to improve if TODGA or TEHDGA is used in place of m-CMPO for large-scale CLEAR processing of 241 Am.

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Section: ■ Results and Discussionmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

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Characterizing Extraction Chromatography for Large-Scale Americium-241 Processing

Arko

Dan

Adelman

et al. 2021

Ind. Eng. Chem. Res.

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“…The 13 C and 1 H NMR data, available from the authors, are little changed from the resonances for the free ligand. 12 The ketonic group has resonances in the range at 165.6 to 166.0 ppm, i.e. no discernable influence of the metal coordination for complexes 3, 4 and 5.…”

Section: Spectroscopic Characterizationmentioning

confidence: 99%

“…1 -11 We recently reported an efficient, relatively large-scale, one-pot synthesis of a hydrophobic example of this class of material, di(p-tert-butylphenyl)-N,N-di-iso-butylcarbamoylmethylphosphine oxide (1), 12 an extractant that has proven qualities for large-scale actinide extraction. 13 Several structures of related CMPO complexes of the actinides, lanthanides and transition metals have been reported, 14 -18 but to our knowledge no main group complexes are known.…”

Section: Introductionmentioning

confidence: 99%

Di(p‐tert‐butylphenyl)‐N,N‐di‐(iso‐butyl)carbamoylmethylphosphine oxide and its organotin and uranyl adducts: structural and spectroscopic characterization

Kapoor

Guillory

Schulte

et al. 2005

Applied Organom Chemis

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The single-crystal structure of the hydrophobic actinide extractant di(p-tert-butylphenyl)-N,N-di-(isobutyl)carbamoylmethylphosphine oxide (CMPO, 1) has been determined, as has that of its 1 : 1 chelate complex with uranyl nitrate (2), its 1 : 1 monodentate complexes with Ph 3 SnCl (3) and Me 2 SnCl 2 (4) bonding via the P O group. A 1 : 1 bidentate complex with Ph 2 SnCl 2 bonding via both P O and C O functionalities (5) was obtained which in solution exhibits a C O → Sn bond dissociation to exist as the monodentate isomer coordinating only through the P O group.

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