Stable Actinide π Complexes of a Neutral 1,4‐Diborabenzene |
| |
Authors: | Valerie Paprocki,Peter Hrob rik,Katie L. M. Harriman,Martin S. Luff,Thomas Kupfer,Martin Kaupp,Muralee Murugesu,Holger Braunschweig |
| |
Affiliation: | Valerie Paprocki,Peter Hrobárik,Katie L. M. Harriman,Martin S. Luff,Thomas Kupfer,Martin Kaupp,Muralee Murugesu,Holger Braunschweig |
| |
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 ThCl4(dme)2 or UCl4, 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. |
| |
Keywords: | actinides bonding boron heterocycles π complexes |
|
|