Year: 2021
Type: article
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.
Source: Chemical Science
DOI: 10.1039/d1sc01007g
Authors: Joseph F. DeJesus, Ryan W. F. Kerr, Deborah A. Penchoff, Xian B. Carroll, Charles C. Peterson, Polly L. Arnold, David M. Jenkins
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: diamond
Funders: U.S. Department of Energy, National Energy Research Scientific Computing Center, European Commission, University of Edinburgh, Office of Science, Engineering and Physical Sciences Research Council, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Lawrence Berkeley National Laboratory
Awards: G1079818582, G1143651532, G122673668, G1286236842, G1286251239, G1414775356, G1445641779, G1677143136, G1816284028, G2037563265, G2857863752, G2880384052, G30714459, G3083819904, G3327601824, G365575497, G419881185, G42916606, G434337789, G4480586979, G4501827968, G465867758, G498139845, G5076365615, G526230902, G5296923526, G5849692847, G622401174, G650090426, G654302390, G7354628648, EPSRC Centre for Doctoral Training in Critical Resource Catalysis - CRITICAT, G805243471, G969749505, G969889393
OpenAlex ID: W3163913805