In:
Angewandte Chemie International Edition, Wiley, Vol. 59, No. 31 ( 2020-07-27), p. 13109-13115
Abstract:
The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d‐block and f‐block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora‐π‐aromatics are less prevalent particularly for the f‐block, due to less effective metal‐to‐ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong π donor capabilities of a neutral 1,4‐diborabenzene. A series of remarkably robust, π‐coordinated thorium(IV) and uranium(IV) half‐sandwich complexes were synthesized by simply combining the bora‐π‐aromatic with ThCl 4 (dme) 2 or UCl 4 , representing the first examples of actinide complexes with a neutral boracycle as sandwich‐type ligand. Experimental and computational studies showed that the strong actinide–heteroarene interactions are predominately electrostatic in nature with distinct ligand‐to‐metal π donation and without significant π/δ backbonding contributions.
Type of Medium:
Online Resource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.202004501
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
2011836-3
detail.hit.zdb_id:
123227-7