Issue 22, 2021

Actinide tetra-N-heterocyclic carbene ‘sandwiches’


Highly-symmetrical, thorium and uranium octakis-carbene ‘sandwich’ complexes have been prepared by ‘sandwiching’ the An(IV) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms. The complexes were characterized by a range of experimental methods and DFT calculations. X-ray crystallography confirms the geometry at the metal centre can be set by the size of the macrocyclic ring, leading to either square prismatic or square anti-prismatic shapes; the geometry of the latter is retained in solution, which also undergoes reversible, electrochemical one-electron oxidation or reduction for the uranium variant. DFT calculations reveal a frontier orbital picture that is similar to thorocene and uranocene, in which the NHC ligands show almost exclusively σ-donation to the metal without π-backbonding.

Graphical abstract: Actinide tetra-N-heterocyclic carbene ‘sandwiches’

Supplementary files

Article information

Article type
Edge Article
19 Feb 2021
15 Apr 2021
First published
10 May 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 7882-7887

Actinide tetra-N-heterocyclic carbene ‘sandwiches’

J. F. DeJesus, R. W. F. Kerr, D. A. Penchoff, X. B. Carroll, C. C. Peterson, P. L. Arnold and D. M. Jenkins, Chem. Sci., 2021, 12, 7882 DOI: 10.1039/D1SC01007G

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