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research article

Cation assisted binding and cleavage of dinitrogen by uranium complexes

Jori, Nadir  
•
Rajeshkumar, Thayalan
•
Scopelliti, Rosario  
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July 14, 2022
Chemical Science

The role of alkali promoters in N-2 cleavage by metal complexes remains poorly understood despite its relevance to the industrial production of ammonia from N-2. Here we report a series of alkali bound-oxo-bridged diuranium(iii) complexes that provide a unique example of decreasing N-2 binding affinity with increasing cation size (from K to Cs). N-2 binding was found to be irreversible in the presence of K. A N-2 complex could be isolated in the solid state in the presence of the Rb cation and crystallographically characterized, but N-2 binding was found to be reversible under vacuum. In the presence of the Cs cation N-2 binding could not be detected at 1 atm. Electrochemical and Computational studies suggest that the decrease in N-2 binding affinity is due to steric rather than electronic effects. We also find that weak N-2 binding in ambient conditions does not prevent alkali assisted N-2 cleavage to nitride from occurring. More importantly, we present the first example of cesium assisted N-2 cleavage leading to the isolation of a N-2 derived multimetallic U/Cs bis-nitride. The nitrides readily react with protons and CO to yield ammonia, cyanate and cyanide.

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Type
research article
DOI
10.1039/d2sc02530b
Web of Science ID

WOS:000828708000001

Author(s)
Jori, Nadir  
Rajeshkumar, Thayalan
Scopelliti, Rosario  
Zivkovic, Ivica  
Sienkiewicz, Andrzej  
Maron, Laurent
Mazzanti, Marinella  
Date Issued

2022-07-14

Publisher

ROYAL SOC CHEMISTRY

Published in
Chemical Science
Volume

13

Issue

32

Start page

9232

End page

9242

Subjects

Chemistry, Multidisciplinary

•

Chemistry

•

multiple bond formation

•

multimetallic cooperativity

•

magnetic communication

•

stepwise reduction

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nitride

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activation

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ammonia

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n-2

•

hydrogenation

•

ligand

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
SCI-SB-MM  
Available on Infoscience
August 1, 2022
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/189651
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