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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 [(C5 Me 5)2U(μ-H)]2

Journal Article · · Organometallics
 [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
+ Show Author Affiliations

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).

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); US Department of Homeland Security (DHS)
Grant/Contract Number:
AC52-06NA25396; CHE-1265608; 2012-DN-130-NF0001
OSTI ID:
1400122
Report Number(s):
LA-UR-15-28978
Journal Information:
Organometallics, Vol. 35, Issue 5; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science

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Cited By (8)

Intrinsic reactivity of a uranium metallacyclopropene toward unsaturated organic molecules journal January 2016
Actinide 2-metallabiphenylenes that satisfy Hückel’s rule journal February 2020
Investigation of N-Heterocyclic Carbene-Supported Group 12 Triflates as Pre-catalysts for Hydrosilylation/Borylation journal October 2016
Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex journal March 2018
A Sterically Biased Unsymmetrical Azobenzene Derivative: Synthesis, Molecular Structure, and 15N NMR Spectroscopic Analysis of (E)-1-(2,6-Diisopropylphenyl)-2-phenyldiazine journal October 2017
Preparation of a uranium metallacyclocumulene and its reactivity towards unsaturated organic molecules journal January 2017
A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium( vi ) monosulphide, uranium( vi ) η 2 -disulphide, and uranium( iv ) phosphine sulphide complexes journal January 2019
Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex journal March 2018

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