Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb)

Samantha K. Cary; Maksim Livshits; Justin N. Cross; Maryline G. Ferrier; Veronika Mocko; Benjamin W. Stein; Stosh A. Kozimor; Brian L. Scott; Jeffrey J. Rack

doi:10.1021/acs.inorgchem.7b03089

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA^-); Synthesis and Structure of M^IVTTA₄ (M^IV = Zr, Hf, Ce, Th, U, Np, Pu) and M^III(TTA)₄^- (M^III = Ce, Nd, Sm, Yb)

Samantha K. Cary, Maksim Livshits, Justin N. Cross, Maryline G. Ferrier, Veronika Mocko, Benjamin W. Stein, Stosh A. Kozimor, Brian L. Scott, Jeffrey J. Rack

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction - or find alternatives - because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M^IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M^III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M^IV(TTA)₄. Meanwhile, +3 metals formed anionic M^III(TTA)₄^- species. Characterization of these M(TTA)₄^x- (x = 0, 1) compounds by UV-vis-NIR, IR, ¹H and ¹⁹F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np^IV(TTA)₄ and Pu^IV(TTA)₄ were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M^IV(TTA)₄ and M^III(TTA)₄^- are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np ^IV to Pu^IV, Hf^IV, and Zr^IV.

Original language	English
Pages (from-to)	3782-3797
Number of pages	16
Journal	Inorganic Chemistry
Volume	57
Issue number	7
DOIs	https://doi.org/10.1021/acs.inorgchem.7b03089
State	Published - Apr 2 2018
Externally published	Yes

Funding

We gratefully recognize the Heavy Element Chemistry Program at Los Alamos National Laboratory (LANL) by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE) (S.A.K., V.M., B.L.S.) and the U.S. Department of Energy. LANL is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of U.S. DOE (Contract No. DE-AC52-06NA25396). Portions of this work were supported by postdoctoral fellowships from the Glenn T. Seaborg Institute (M.G.F., B.W.S.) and the LDRD office, named fellowship program; Marie Curie Distinguished Postdoctoral Fellowship (S.K.C.). J.J.R. acknowledges National Science Foundation (Grant No. CHE 1602240) for financial support. Use of the Stanford Synchrotron Radiation Light-source (SSRL), SLAC National Accelerator Laboratory, was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research and by the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393).

Funders	Funder number
Glenn T. Seaborg Institute
National Nuclear Security Administration of U.S. DOE	DE-AC52-06NA25396
National Science Foundation	CHE 1602240
National Institutes of Health
U.S. Department of Energy
National Institute of General Medical Sciences	P41GM103393
Office of Science	DE-AC02-76SF00515
Basic Energy Sciences
Biological and Environmental Research
Los Alamos National Laboratory
SLAC National Accelerator Laboratory
Chemical Sciences, Geosciences, and Biosciences Division

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Cary, S. K., Livshits, M., Cross, J. N., Ferrier, M. G., Mocko, V., Stein, B. W., Kozimor, S. A., Scott, B. L., & Rack, J. J. (2018). Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA^-); Synthesis and Structure of M^IVTTA₄ (M^IV = Zr, Hf, Ce, Th, U, Np, Pu) and M^III(TTA)₄^- (M^III = Ce, Nd, Sm, Yb). Inorganic Chemistry, 57(7), 3782-3797. https://doi.org/10.1021/acs.inorgchem.7b03089

@article{e3724d92f0984f8a9aba9374ca2aa0e4,

title = "Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb)",

abstract = "Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction - or find alternatives - because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (MIV = Zr, Hf, Ce, Th, U, Np, and Pu vs MIII = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula MIV(TTA)4. Meanwhile, +3 metals formed anionic MIII(TTA)4- species. Characterization of these M(TTA)4x- (x = 0, 1) compounds by UV-vis-NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that NpIV(TTA)4 and PuIV(TTA)4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between MIV(TTA)4 and MIII(TTA)4- are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to PuIV, HfIV, and ZrIV.",

author = "Cary, {Samantha K.} and Maksim Livshits and Cross, {Justin N.} and Ferrier, {Maryline G.} and Veronika Mocko and Stein, {Benjamin W.} and Kozimor, {Stosh A.} and Scott, {Brian L.} and Rack, {Jeffrey J.}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = apr,

day = "2",

doi = "10.1021/acs.inorgchem.7b03089",

language = "English",

volume = "57",

pages = "3782--3797",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

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Cary, SK, Livshits, M, Cross, JN, Ferrier, MG, Mocko, V, Stein, BW, Kozimor, SA, Scott, BL & Rack, JJ 2018, 'Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA^-); Synthesis and Structure of M^IVTTA₄ (M^IV = Zr, Hf, Ce, Th, U, Np, Pu) and M^III(TTA)₄^- (M^III = Ce, Nd, Sm, Yb)', Inorganic Chemistry, vol. 57, no. 7, pp. 3782-3797. https://doi.org/10.1021/acs.inorgchem.7b03089

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA^-); Synthesis and Structure of M^IVTTA₄ (M^IV = Zr, Hf, Ce, Th, U, Np, Pu) and M^III(TTA)₄^- (M^III = Ce, Nd, Sm, Yb). / Cary, Samantha K.; Livshits, Maksim; Cross, Justin N. et al.
In: Inorganic Chemistry, Vol. 57, No. 7, 02.04.2018, p. 3782-3797.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb)

AU - Cary, Samantha K.

AU - Livshits, Maksim

AU - Cross, Justin N.

AU - Ferrier, Maryline G.

AU - Mocko, Veronika

AU - Stein, Benjamin W.

AU - Kozimor, Stosh A.

AU - Scott, Brian L.

AU - Rack, Jeffrey J.

PY - 2018/4/2

Y1 - 2018/4/2

N2 - Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction - or find alternatives - because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (MIV = Zr, Hf, Ce, Th, U, Np, and Pu vs MIII = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula MIV(TTA)4. Meanwhile, +3 metals formed anionic MIII(TTA)4- species. Characterization of these M(TTA)4x- (x = 0, 1) compounds by UV-vis-NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that NpIV(TTA)4 and PuIV(TTA)4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between MIV(TTA)4 and MIII(TTA)4- are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to PuIV, HfIV, and ZrIV.

AB - Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction - or find alternatives - because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (MIV = Zr, Hf, Ce, Th, U, Np, and Pu vs MIII = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula MIV(TTA)4. Meanwhile, +3 metals formed anionic MIII(TTA)4- species. Characterization of these M(TTA)4x- (x = 0, 1) compounds by UV-vis-NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that NpIV(TTA)4 and PuIV(TTA)4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between MIV(TTA)4 and MIII(TTA)4- are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to PuIV, HfIV, and ZrIV.

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U2 - 10.1021/acs.inorgchem.7b03089

DO - 10.1021/acs.inorgchem.7b03089

M3 - Article

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AN - SCOPUS:85044730125

SN - 0020-1669

VL - 57

SP - 3782

EP - 3797

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA^-); Synthesis and Structure of M^IVTTA₄ (M^IV = Zr, Hf, Ce, Th, U, Np, Pu) and M^III(TTA)₄^- (M^III = Ce, Nd, Sm, Yb)

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