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Title: Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C 5 Me 5) 2U(μ-H)] 2

Here, this work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C 5Me 5) 2U–H] x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C 5Me5)2UMe2 (4) with 2 equiv of phenylsilane at 50 °C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C 5Me 5) 2U(H)(μ-H)] 2 (2), which was harnessed to prepare a variety of organometallic complexes, including (C 5Me 5) 2U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C 5Me 5) 2U(C 4Me 4) (11).
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [4] ;  [5] ;  [4]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
  3. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  5. Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
LA-UR-15-28978
Journal ID: ISSN 0276-7333
Grant/Contract Number:
AC52-06NA25396; CHE-1265608; 2012-DN-130-NF0001
Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 35; Journal Issue: 5; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); US Department of Homeland Security (DHS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
OSTI Identifier:
1400122

Pagano, Justin K., Dorhout, Jacquelyn M., Czerwinski, Kenneth R., Morris, David E., Scott, Brian L., Waterman, Rory, and Kiplinger, Jaqueline L.. Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5 Me 5)2U(μ-H)]2. United States: N. p., Web. doi:10.1021/acs.organomet.6b00091.
Pagano, Justin K., Dorhout, Jacquelyn M., Czerwinski, Kenneth R., Morris, David E., Scott, Brian L., Waterman, Rory, & Kiplinger, Jaqueline L.. Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5 Me 5)2U(μ-H)]2. United States. doi:10.1021/acs.organomet.6b00091.
Pagano, Justin K., Dorhout, Jacquelyn M., Czerwinski, Kenneth R., Morris, David E., Scott, Brian L., Waterman, Rory, and Kiplinger, Jaqueline L.. 2016. "Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5 Me 5)2U(μ-H)]2". United States. doi:10.1021/acs.organomet.6b00091. https://www.osti.gov/servlets/purl/1400122.
@article{osti_1400122,
title = {Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5 Me 5)2U(μ-H)]2},
author = {Pagano, Justin K. and Dorhout, Jacquelyn M. and Czerwinski, Kenneth R. and Morris, David E. and Scott, Brian L. and Waterman, Rory and Kiplinger, Jaqueline L.},
abstractNote = {Here, this work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C5Me5)2U–H]x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C5Me5)2UMe2 (4) with 2 equiv of phenylsilane at 50 °C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C5Me5)2U(H)(μ-H)]2 (2), which was harnessed to prepare a variety of organometallic complexes, including (C5Me5)2U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C5Me5)2U(C4Me4) (11).},
doi = {10.1021/acs.organomet.6b00091},
journal = {Organometallics},
number = 5,
volume = 35,
place = {United States},
year = {2016},
month = {3}
}