Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes

Karla A. Erickson; Alejandro G. Lichtscheidl; Marisa J. Monreal; Andrew T. Nelson; Brian L. Scott; David E. Morris; Jaqueline L. Kiplinger

doi:10.1016/j.jorganchem.2017.10.044

Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes

Karla A. Erickson, Alejandro G. Lichtscheidl, Marisa J. Monreal, Andrew T. Nelson, Brian L. Scott, David E. Morris, Jaqueline L. Kiplinger

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

2 Scopus citations

Abstract

The terminal actinide fluoride bonds in (C₅Me₅)₂ThF₂(py) (py = pyridine) and (C₅Me₅)₂UF₂(O=PR₃) (R = Me, Ph) react with two equivalents of Me₃SiN₃ in toluene to form the polymeric thorium bis(azide), [(C₅Me₅)₂Th(N₃)₂]_∞, and a new class of monometallic uranium bis(azide) complexes, (C₅Me₅)₂U(N₃)₂(O=PR₃), respectively. Full characterization of the novel complexes (C₅Me₅)₂ThF₂(py) and (C₅Me₅)₂UF₂(O=PR₃) are reported, including the solid-state structures of (C₅Me₅)₂ThF₂(py) and (C₅Me₅)₂U(N₃)₂(O=PPh₃). Electronic absorption spectral data are also reported for (C₅Me₅)₂AnF₂(py) (An = Th, U) and (C₅Me₅)₂U(N₃)₂(O=PR₃) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.

Original language	English
Pages (from-to)	180-186
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	857
DOIs	https://doi.org/10.1016/j.jorganchem.2017.10.044
State	Published - Feb 15 2018
Externally published	Yes

Funding

For financial support of this work, we acknowledge the U.S. Department of Energy through the Los Alamos G. T. Seaborg Institute for Transactinium Science (Postdoctoral Fellowships to K.A.E., M.J.M., and A.G.L.), Los Alamos National Laboratory (Director and Reines PD fellowships to M.J.M.), the Advanced Fuels Campaign Fuel Cycle Research & Development Program (A.T.N.), and the LANL LDRD Program. Los Alamos National Laboratory is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration (contract DE-AC52-06NA25396 ).

Keywords

Azide
Electronic absorption spectroscopy
Fluoride
Thorium
Uranium
X-ray crystallography

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10.1016/j.jorganchem.2017.10.044

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Erickson, K. A., Lichtscheidl, A. G., Monreal, M. J., Nelson, A. T., Scott, B. L., Morris, D. E., & Kiplinger, J. L. (2018). Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes. Journal of Organometallic Chemistry, 857, 180-186. https://doi.org/10.1016/j.jorganchem.2017.10.044

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title = "Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes",

abstract = "The terminal actinide fluoride bonds in (C5Me5)2ThF2(py) (py = pyridine) and (C5Me5)2UF2(O=PR3) (R = Me, Ph) react with two equivalents of Me3SiN3 in toluene to form the polymeric thorium bis(azide), [(C5Me5)2Th(N3)2]∞, and a new class of monometallic uranium bis(azide) complexes, (C5Me5)2U(N3)2(O=PR3), respectively. Full characterization of the novel complexes (C5Me5)2ThF2(py) and (C5Me5)2UF2(O=PR3) are reported, including the solid-state structures of (C5Me5)2ThF2(py) and (C5Me5)2U(N3)2(O=PPh3). Electronic absorption spectral data are also reported for (C5Me5)2AnF2(py) (An = Th, U) and (C5Me5)2U(N3)2(O=PR3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.",

keywords = "Azide, Electronic absorption spectroscopy, Fluoride, Thorium, Uranium, X-ray crystallography",

author = "Erickson, {Karla A.} and Lichtscheidl, {Alejandro G.} and Monreal, {Marisa J.} and Nelson, {Andrew T.} and Scott, {Brian L.} and Morris, {David E.} and Kiplinger, {Jaqueline L.}",

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Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes. / Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa J. et al.
In: Journal of Organometallic Chemistry, Vol. 857, 15.02.2018, p. 180-186.

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

TY - JOUR

T1 - Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes

AU - Erickson, Karla A.

AU - Lichtscheidl, Alejandro G.

AU - Monreal, Marisa J.

AU - Nelson, Andrew T.

AU - Scott, Brian L.

AU - Morris, David E.

AU - Kiplinger, Jaqueline L.

PY - 2018/2/15

Y1 - 2018/2/15

N2 - The terminal actinide fluoride bonds in (C5Me5)2ThF2(py) (py = pyridine) and (C5Me5)2UF2(O=PR3) (R = Me, Ph) react with two equivalents of Me3SiN3 in toluene to form the polymeric thorium bis(azide), [(C5Me5)2Th(N3)2]∞, and a new class of monometallic uranium bis(azide) complexes, (C5Me5)2U(N3)2(O=PR3), respectively. Full characterization of the novel complexes (C5Me5)2ThF2(py) and (C5Me5)2UF2(O=PR3) are reported, including the solid-state structures of (C5Me5)2ThF2(py) and (C5Me5)2U(N3)2(O=PPh3). Electronic absorption spectral data are also reported for (C5Me5)2AnF2(py) (An = Th, U) and (C5Me5)2U(N3)2(O=PR3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.

AB - The terminal actinide fluoride bonds in (C5Me5)2ThF2(py) (py = pyridine) and (C5Me5)2UF2(O=PR3) (R = Me, Ph) react with two equivalents of Me3SiN3 in toluene to form the polymeric thorium bis(azide), [(C5Me5)2Th(N3)2]∞, and a new class of monometallic uranium bis(azide) complexes, (C5Me5)2U(N3)2(O=PR3), respectively. Full characterization of the novel complexes (C5Me5)2ThF2(py) and (C5Me5)2UF2(O=PR3) are reported, including the solid-state structures of (C5Me5)2ThF2(py) and (C5Me5)2U(N3)2(O=PPh3). Electronic absorption spectral data are also reported for (C5Me5)2AnF2(py) (An = Th, U) and (C5Me5)2U(N3)2(O=PR3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.

KW - Azide

KW - Electronic absorption spectroscopy

KW - Fluoride

KW - Thorium

KW - Uranium

KW - X-ray crystallography

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M3 - Article

AN - SCOPUS:85034856881

SN - 0022-328X

VL - 857

SP - 180

EP - 186

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Exploiting the reactivity of actinide fluoride bonds for the synthesis and characterization of a new class of monometallic bis(azide) uranium complexes

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Keywords

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