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research article

Isolation and redox reactivity of cerium complexes in four redox states

Hsueh, Fang-Che  
•
Rajeshkumar, Thayalan
•
Maron, Laurent
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May 5, 2023
Chemical Science

The chemistry of lanthanides is limited to one electron transfer reactions due to the difficulty of accessing multiple oxidation states. Here we report that a redox-active ligand combining three siloxides with an arene ring in a tripodal ligand can stabilize cerium complexes in four different redox states and can promote multielectron redox reactivity in cerium complexes. Ce(iii) and Ce(iv) complexes [(LO3)Ce(THF)] (1) and [(LO3)CeCl] (2) (LO3 = 1,3,5-(2-OSi((OBu)-Bu-t)(2)C6H4)(3)C6H3) were synthesized and fully characterized. Remarkably the one-electron reduction and the unprecedented two-electron reduction of the tripodal Ce(iii) complex are easily achieved to yield reduced complexes [K(2.2.2-cryptand)][(LO3)Ce(THF)] (3) and [K-2{(LO3)Ce(Et2O)(3)}] (5) that are formally "Ce(ii)" and "Ce(i)" analogues. Structural analysis, UV and EPR spectroscopy and computational studies indicate that in 3 the cerium oxidation state is in between +II and +III with a partially reduced arene. In 5 the arene is doubly reduced, but the removal of potassium results in a redistribution of electrons on the metal. The electrons in both 3 and 5 are stored onto d-bonds allowing the reduced complexes to be described as masked "Ce(ii)" and "Ce(i)". Preliminary reactivity studies show that these complexes act as masked Ce(ii) and Ce(i) in redox reactions with oxidizing substrates such as Ag+, CO2, I-2 and S-8 effecting both one- and two-electron transfers that are not accessible in classical cerium chemistry.

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Type
research article
DOI
10.1039/d3sc01478a
Web of Science ID

WOS:000989403200001

Author(s)
Hsueh, Fang-Che  
Rajeshkumar, Thayalan
Maron, Laurent
Scopelliti, Rosario  
Sienkiewicz, Andrzej  
Mazzanti, Marinella  
Date Issued

2023-05-05

Published in
Chemical Science
Subjects

Chemistry, Multidisciplinary

•

Chemistry

•

c-h activation

•

reductive disproportionation

•

crystal-structures

•

carbon-dioxide

•

chemistry

•

ligand

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metal

•

series

•

ions

•

lanthanide(iii)

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LQM  
SCI-SB-MM  
FunderGrant Number

FNS

200020_212723

RelationURL/DOI

IsSupplementedBy

https://doi.org/10.5281/zenodo.7869094
Available on Infoscience
June 5, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/198033
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