Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Spectroscopic and Computational Evidence of Uranium Dihydrogen Complexes

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.3c12636· OSTI ID:2318533
 [1];  [2];  [2];  [3];  [4]
  1. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Department of Chemistry, University of California, Berkeley, California 94720-1460, United States; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720-1460, United States
  2. Université de Toulouse (France)
  3. University of California, Berkeley, CA (United States)
  4. University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

Dihydrogen complexation, a phenomenon with robust precedent in the transition metal series, is spectroscopically detected for a uranium(III) complex and thereby extended for the first time to the 5f series. The vacant coordination site and low valence of (C5H4SiMe3)3U prove to be key to the reversible formation of (C5H4SiMe3)3U–H2 (complex 1), and the paramagnetism of the f3 center facilitates the detection of complex 1 by NMR spectroscopy. Density functional theory calculations reveal that the delocalization of the 5f electron density from (C5H4SiMe3)3U onto the side-on dihydrogen ligand is crucial to complex formation, an unusual bonding situation for an actinide acid–base complex. Here, the spectroscopic and computational results are compared to those reported for lanthanide metallocenes to yield insight into the nature of–and future possibilities for–f-element dihydrogen complexation.

Research Organization:
University of California, Berkeley, CA (United States); Université de Toulouse (France); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
NA0003996; AC02-05CH11231
OSTI ID:
2318533
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 2 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (35)

Carbon Monoxide and Isocyanide Complexes of Trivalent Uranium Metallocenes journal October 1999
Characterizing Pressure-Induced Uranium CH Agostic Bonds journal April 2015
Uranocenium: Synthesis, Structure, and Chemical Bonding journal June 2019
From Molecular Complexes to Complex Metallic Nanostructures—2H Solid‐State NMR Studies of Ruthenium‐Containing Hydrogenation Catalysts journal May 2013
NMR analyses of molecular conformations and conformational equilibria with the lanthanide probe method journal January 1980
Metal–dihydrogen and σ-bond coordination: the consummate extension of the Dewar–Chatt–Duncanson model for metal–olefin π bonding journal October 2001
Trivalent uranium chemistry: molecular structure of [(Me3Si)2N]3U journal March 1998
Activation of dihydrogen and coordination of molecular H2 on transition metals journal February 2014
Dihydrogen Complexation journal March 2016
Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides journal June 2016
σ-H–H, σ-C–H, and σ-Si–H Bond Activation Catalyzed by Metal Nanoparticles journal October 2019
Structural, Electrochemical, and Magnetic Studies of Bulky Uranium(III) and Uranium(IV) Metallocenes journal November 2019
Fundamentals of H 2 Binding and Reactivity on Transition Metals Underlying Hydrogenase Function and H 2 Production and Storage journal October 2007
Challenges for Density Functional Theory journal December 2011
Synthesis and Single Crystal X-ray Diffraction Study on the First Isolable Carbonyl Complex of an Actinide, (C5Me4H)3U(CO) journal March 1995
Bonding in tris(.eta.5-cyclopentadienyl) actinide complexes. 2. The ground electronic configurations of "base-free" Cp3An complexes (An = thorium, protactinium, uranium, neptunium, plutonium) journal April 1989
Spectroscopic detection of organolanthanide dihydrogen and olefin complexes journal October 1989
Metal, bond energy, and ancillary ligand effects on actinide-carbon .sigma.-bond hydrogenolysis. A kinetic and mechanistic study journal December 1987
Preparation of the first molecular carbon monoxide complex of uranium, (Me3SiC5H4)3UCO journal January 1986
Reversible Binding and Reduction of Dinitrogen by a Uranium(III) Pentalene Complex journal August 2002
A Monometallic f Element Complex of Dinitrogen:  (C 5 Me 5 ) 3 U(η 1 -N 2 ) journal November 2003
Evidence for Alkane Coordination to an Electron-Rich Uranium Center journal December 2003
Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C 5 H 4 SiMe 3 ) 3 U] journal August 2013
Complex of Dinitrogen with Trivalent Uranium journal January 1998
Heterodinuclear Uranium/Molybdenum Dinitrogen Complexes journal June 1998
Expanding Thorium Hydride Chemistry Through Th 2+ , Including the Synthesis of a Mixed-Valent Th 4+ /Th 3+ Hydride Complex journal March 2016
Ethene Activation and Catalytic Hydrogenation by a Low-Valent Uranium Pentalene Complex journal December 2019
Crystal structures of (MeC5H4)3ML [M = uranium or cerium; L = quinuclidine or P(OCH2)3CEt]. Evidence for uranium to phosphorus .pi.-back-bonding journal June 1988
First example of a neutral homoleptic uranium alkyl. Synthesis, properties, and structure of U[CH(SiMe3)2]3 journal March 1989
Bonding of H2, N2, Ethylene, and Acetylene to Bivalent Lanthanide Metallocenes:  Trends from DFT Calculations on Cp2M and Cp*2 M (M = Sm, Eu, Yb) and Experiments with Cp*2Yb journal November 2003
The Bond between CO and Cp′ 3 U in Cp′ 3 U(CO) Involves Back-bonding from the Cp′ 3 U Ligand-Based Orbitals of π-Symmetry, where Cp′ Represents a Substituted Cyclopentadienyl Ligand journal July 2009
Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules journal July 2022
Synthesis, structure, and reactivity of crystalline molecular complexes of the {[C 5 H 3 (SiMe 3 ) 2 ] 3 Th} 1− anion containing thorium in the formal +2 oxidation state journal January 2015
Isolation of C1 through C4 derivatives from CO using heteroleptic uranium(iii) metallocene aryloxide complexes journal January 2023
Cooperative dihydrogen activation with unsupported uranium–metal bonds and characterization of a terminal U(iv) hydride journal January 2023

Similar Records

Spectroscopic detection of organolanthanide dihydrogen and olefin complexes
Journal Article · Wed Oct 25 00:00:00 EDT 1989 · Journal of the American Chemical Society; (USA) · OSTI ID:6717478
Chemistry of trivalent uranium metallocenes: electron-transfer reactions with carbon disulfide. Formation of ((RC/sub 5/H/sub 4/)/sub 3/U)/sub 2/(. mu. -eta/sup 1/,eta/sup 2/-CS/sub 2/)
Journal Article · Wed May 21 00:00:00 EDT 1986 · Inorg. Chem.; (United States) · OSTI ID:5657992

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Uranium
dihydrogen complexes
ligands
molecular interactions