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Actinide tetra-N-heterocyclic carbene 'sandwiches'.

ABSTRACT: 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.

SUBMITTER: DeJesus JF

PROVIDER: S-EPMC8188502 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Actinide tetra-N-heterocyclic carbene 'sandwiches'.

DeJesus Joseph F JF Kerr Ryan W F RWF Penchoff Deborah A DA Carroll Xian B XB Peterson Charles C CC Arnold Polly L PL Jenkins David M DM

Chemical science 20210510 22

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-prismat ...[more]

PMID: 34168841

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