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Title: Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes

The terminal actinide fluoride bonds in (C 5Me 5) 2ThF 2(py) (py = pyridine) and (C 5Me 5) 2UF 2(O=PR 3) (R = Me, Ph) react with two equivalents of Me 3SiN 3 in toluene to form the polymeric thorium bis(azide), [(C 5Me 5) 2Th(N 3)2] , and a new class of monometallic uranium bis(azide) complexes, (C 5Me 5) 2U(N 3)2(O=PR 3), respectively. Full characterization of the novel complexes (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2UF 2(O=PR 3) are reported, including the solid-state structures of (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2U(N 3) 2(O=PPh 3). Lastly, electronic absorption spectral data are also reported for (C 5Me 5) 2AnF 2(py) (An = Th, U) and (C 5Me 5) 2U(N 3) 2(O=PR 3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.
Authors:
ORCiD logo [1] ;  [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Report Number(s):
LA-UR-17-28097
Journal ID: ISSN 0022-328X; TRN: US1800386
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Journal of Organometallic Chemistry
Additional Journal Information:
Journal Volume: 857; Journal ID: ISSN 0022-328X
Publisher:
Elsevier
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Thorium; Uranium; Fluoride; Azide; Electronic absorption spectroscopy; X-ray crystallography
OSTI Identifier:
1412873

Erickson, Karla A., Lichtscheidl, Alejandro G., Monreal, Marisa Jennifer, Nelson, Andrew Thomas, Scott, Brian Lindley, Morris, David Edwin, and Kiplinger, Jaqueline Loetsch. Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes. United States: N. p., Web. doi:10.1016/j.jorganchem.2017.10.044.
Erickson, Karla A., Lichtscheidl, Alejandro G., Monreal, Marisa Jennifer, Nelson, Andrew Thomas, Scott, Brian Lindley, Morris, David Edwin, & Kiplinger, Jaqueline Loetsch. Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes. United States. doi:10.1016/j.jorganchem.2017.10.044.
Erickson, Karla A., Lichtscheidl, Alejandro G., Monreal, Marisa Jennifer, Nelson, Andrew Thomas, Scott, Brian Lindley, Morris, David Edwin, and Kiplinger, Jaqueline Loetsch. 2017. "Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes". United States. doi:10.1016/j.jorganchem.2017.10.044. https://www.osti.gov/servlets/purl/1412873.
@article{osti_1412873,
title = {Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes},
author = {Erickson, Karla A. and Lichtscheidl, Alejandro G. and Monreal, Marisa Jennifer and Nelson, Andrew Thomas and Scott, Brian Lindley and Morris, David Edwin and Kiplinger, Jaqueline Loetsch},
abstractNote = {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). Lastly, 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.},
doi = {10.1016/j.jorganchem.2017.10.044},
journal = {Journal of Organometallic Chemistry},
number = ,
volume = 857,
place = {United States},
year = {2017},
month = {11}
}