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Title: Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry Division
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Physics and Applications Division
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Science and Technology Division
Publication Date:
Report Number(s):
LA-UR-15-27740
Journal ID: ISSN 2304-6740
Grant/Contract Number:
AC52-06NA25396; AC05-06OR23100
Type:
Accepted Manuscript
Journal Name:
Inorganics
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2304-6740
Publisher:
MDPI
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Heavy Element Chemistry Program; USDOE Office of Nuclear Energy (NE), Fuel Cycle Technologies (NE-5). Fuel Cycle Research and Development Program
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; trivalent and tetravalent uranium; bromide; organometallic
OSTI Identifier:
1335598

Lichtscheidl, Alejandro Gaston, Pagano, Justin K., Scott, Brian Lindley, Nelson, Andrew Thomas, and Kiplinger, Jaqueline Loetsch. Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et). United States: N. p., Web. doi:10.3390/inorganics4010001.
Lichtscheidl, Alejandro Gaston, Pagano, Justin K., Scott, Brian Lindley, Nelson, Andrew Thomas, & Kiplinger, Jaqueline Loetsch. Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et). United States. doi:10.3390/inorganics4010001.
Lichtscheidl, Alejandro Gaston, Pagano, Justin K., Scott, Brian Lindley, Nelson, Andrew Thomas, and Kiplinger, Jaqueline Loetsch. 2016. "Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)". United States. doi:10.3390/inorganics4010001. https://www.osti.gov/servlets/purl/1335598.
@article{osti_1335598,
title = {Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)},
author = {Lichtscheidl, Alejandro Gaston and Pagano, Justin K. and Scott, Brian Lindley and Nelson, Andrew Thomas and Kiplinger, Jaqueline Loetsch},
abstractNote = {The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C5Me4R)2UCl2 (R = Me, Et) with Me3SiBr. Treatment of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with K(O-2,6-iPr2C6H3) afforded the halide aryloxide mixed-ligand complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(X) (R = Me, Et; X = Cl, Br). Complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(Br) (R = Me, Et) can also be synthesized by treating (C5Me4R)2U(O-2,6-iPr2C6H3)(Cl) (R = Me, Et) with Me3SiBr, respectively. Reduction of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with KC8 led to isolation of uranium(III) “ate” species [K(THF)][(C5Me5)2UX2] (X = Cl, Br) and [K(THF)0.5][(C5Me4Et)2UX2] (X = Cl, Br), which can be converted to the neutral complexes (C5Me4R)2U[N(SiMe3)2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.},
doi = {10.3390/inorganics4010001},
journal = {Inorganics},
number = 1,
volume = 4,
place = {United States},
year = {2016},
month = {1}
}