Issue 27, 2023

Synthesis and comparison of iso-structural f-block metal complexes (Ce, U, Np, Pu) featuring η6-arene interactions

Abstract

Reaction of the terphenyl bis(anilide) ligand [{K(DME)2}2LAr] (LAr = {C6H4[(2,6-iPr2C6H3)NC6H4]2}2−) with trivalent chloride “MCl3” salts (M = Ce, U, Np) yields two distinct products; neutral LArM(Cl)(THF) (1M) (M = Np, Ce), and the “-ate” complexes [K(DME)2][(LAr)Np(Cl)2] (2Np) or ([LArM(Cl)2(μ-K(X)2)]) (2Ce, 2U) (M = Ce, U) (X = DME or Et2O) (2M). Alternatively, analogous reactions with the iodide [MI3(THF)4] salts provide access to the neutral compounds LArM(I)(THF) (3M) (M = Ce, U, Np, Pu). All complexes exhibit close arene contacts suggestive of η6-interactions with the central arene ring of the terphenyl backbone, with 3M comprising the first structurally characterized Pu η6-arene moiety. Notably, the metal–arene bond metrics diverge from the predicted trends of metal–carbon interactions based on ionic radii, with the uranium complexes exhibiting the shortest M–Ccentroid distance in all cases. Overall, the data presents a systematic study of f-element M-η6-arene complexes across the early actinides U, Np, Pu, and comparison to cerium congeners.

Graphical abstract: Synthesis and comparison of iso-structural f-block metal complexes (Ce, U, Np, Pu) featuring η6-arene interactions

Supplementary files

Article information

Article type
Edge Article
Submitted
29 apr 2023
Accepted
10 jun 2023
First published
20 jun 2023
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., 2023,14, 7438-7446

Synthesis and comparison of iso-structural f-block metal complexes (Ce, U, Np, Pu) featuring η6-arene interactions

J. Murillo, C. A. P. Goodwin, L. Stevens, S. Fortier, A. J. Gaunt and B. L. Scott, Chem. Sci., 2023, 14, 7438 DOI: 10.1039/D3SC02194G

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