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research article

Nitrogen activation and cleavage by a multimetallic uranium complex

Keener, Megan
•
Fadaei Tirani, Farzaneh  
•
Scopelliti, Rosario  
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July 13, 2022
Chemical Science

Multimetallic-multielectron cooperativity plays a key role in the metal-mediated cleavage of N-2 to nitrides (N3-). In particular, low-valent uranium complexes coupled with strong alkali metal reducing agents can lead to N-2 cleavage, but often, it is ambiguous how many electrons are transferred from the uranium centers to cleave N-2. Herein, we designed new dinuclear uranium nitride complexes presenting a combination of electronically diverse ancillary ligands to promote the multielectron transformation of N-2. Two heteroleptic diuranium nitride complexes, [K{U-IV(OSi((OBu)-Bu-t)(3))(N(SiMe3)(2))(2)}(2)(mu-N)] (1) and [Cs{U-IV(OSi((OBu)-Bu-t)(3))(2)(N(SiMe3)(2))}(2)(mu-N)] (3-Cs), containing different combinations of OSi(CYBu)(3) and N(SiMe3)(2) ancillary ligands, were synthesized. We found that both complexes could be reduced to their U(III)/U(IV) analogues, and the complex, [K-2{U-IV/III(OSi((OBu)-Bu-t)(3))(2)(N(SiMe3)(2))}(2)(mu-N)] (6-K), could be further reduced to a putative U(III)/U(III) species that is capable of promoting the 4e(-) reduction of N-2, yielding the N-2(4-) complex [K-3{U-V(OSi((OBu)-Bu-t)(3))(2)(N(SiMe3)(2)))(2)(mu-N)(mu-eta(2):eta(2)-N-2)], 7. Parallel N-2 reduction pathways were also identified, leading to the isolation of N-2 cleavage products, K-3{U-VI(OSi((OBu)-Bu-t)(3))(2)(N(SiMe3)(2))( N)}(mu-N)(2){U-V(OSi((OBu)-Bu-t)(3))(2)(N(SiMe3)(2))}, 8, and [K-4{(OSi((OBu)-Bu-t)(3))(2)U-V)( N))(mu-NH)(mu-kappa(2):C,N-CH2SiMe2NSiMe3){U-V(OSi((OBu)-Bu-t)(3))(2)]K(N(SiMe3)(2), 9. These complexes provide the first example of N-2 cleavage to nitride by a uranium complex in the absence of reducing alkali metals.

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Type
research article
DOI
10.1039/D2SC02997A
Author(s)
Keener, Megan
Fadaei Tirani, Farzaneh  
Scopelliti, Rosario  
Zivkovic, Ivica
Mazzanti, Marinella  
Date Issued

2022-07-13

Published in
Chemical Science
Volume

13

Issue

27

Start page

8025

End page

8035

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
SCI-SB-MM  
Available on Infoscience
March 16, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/196165
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