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research article

Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides

Hsueh, Fang-Che  
•
Barluzzi, Luciano  
•
Rajeshkumar, Thayalan
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July 23, 2024
Dalton Transactions

Single-atom (group 15 and group 16 anions) bridged dimetallic complexes of low oxidation state uranium provide a convenient route to implement multielectron transfer and promote magnetic communication in uranium chemistry, but remain extremely rare. Here we report the synthesis, redox and magnetic properties of N3-, O2-, and S2- bridged diuranium complexes supported by bulky aryloxide ligands. The U(iv)/U(iv) nitride [Cs(THF)8][(U(OAr)3)2(mu-N)], 1 could be prepared and characterized but could not be reduced. Reduction of the neutral U(iv)/U(iv) complexes [(U(OAr)3)2(mu-X)] A (X = O) and B (X = S) led to the isolation and characterization of the U(iv)/U(iii) and U(iii)/U(iii) analogues. Complexes [(K(THF)4)2(U(OAr)2)2(mu-S)2], 5 and [K(2.2.2-cryptand)]2[(U(OAr)3)2(mu-S)], 6 are the first examples of U(iii) sulphide bridged complexes. Computational studies and redox properties allow the reactivity of the dimetallic complexes to be related to their electronic structure. Reduction of the neutral UIV-X-UIV (X = O or S) complexes supported by aryloxide ligands yielded the UIV/UIII and UIII/UIII analogues. Notably, UIII-S-UIII is the first example of a U(iii) sulphide-bridged complex.

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Type
research article
DOI
10.1039/d4dt01819b
Web of Science ID

WOS:001275720200001

PubMed ID

39051943

Author(s)
Hsueh, Fang-Che  

École Polytechnique Fédérale de Lausanne

Barluzzi, Luciano  

École Polytechnique Fédérale de Lausanne

Rajeshkumar, Thayalan

Universite Federale Toulouse Midi-Pyrenees (ComUE)

Scopelliti, Rosario  

École Polytechnique Fédérale de Lausanne

Zivkovic, Ivica  

École Polytechnique Fédérale de Lausanne

Maron, Lyza G

Universite Federale Toulouse Midi-Pyrenees (ComUE)

Mazzanti, Marinella  

École Polytechnique Fédérale de Lausanne

Date Issued

2024-07-23

Publisher

ROYAL SOC CHEMISTRY

Published in
Dalton Transactions
Volume

53

Issue

32

Start page

13416

End page

13426

Subjects

SMALL-MOLECULE ACTIVATION

•

MULTIPLE BOND FORMATION

•

U-IV-E

•

MAGNETIC COMMUNICATION

•

URANIUM(III) SYNTHESIS

•

ELECTRONIC-STRUCTURE

•

ANSA-DIMETHYLSILYL

•

OXO COMPLEXES

•

NITRIDE

•

REACTIVITY

•

Science & Technology

•

Physical Sciences

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
SCI-SB-MM  
ISIC-XRDSAP  
LQM  
FunderFunding(s)Grant NumberGrant URL

Swiss National Science Foundation (SNSF)

212723

Ecole Polytechnique Federale de Lausanne (EPFL)

Available on Infoscience
January 30, 2025
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/245928
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