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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:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States); Université de Toulouse (France)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; NA0003996
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

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Related Subjects

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