Planar Tetranuclear Uranium Hydride Cluster Supported by ansa‐Bis(cyclopentadienyl) Ligands

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Polynuclear metal hydride clusters play important roles in various catalytic processes, with most of the reported polynuclear metal hydride clusters adopting a polyhedral three‐dimensional structure. Herein, we report the first example of a planar tetranuclear uranium hydride cluster [(CpCMe 2 CMe 2 Cp)U] 4 ( μ 2 ‐H) 4 ( μ 3 ‐H) 4 (U 4 H 8 ). It was synthesized by reacting an ansa ‐bis(cyclopentadienyl) ligand‐supported uranium chloride precursor [(CpCMe 2 CMe 2 Cp)U] 3 ( μ 2 ‐Cl) 3 ( μ 3 ‐Cl) 2 with NaHBEt 3 . The presence of hydrides in U 4 H 8 was confirmed by NMR spectroscopy and its reactivity with phenol and carbon tetrachloride. DFT calculations also facilitated the determination of the hydrides’ positions in U 4 H 8 , featuring four bridging μ 2 ‐H ligands and four face‐capping μ 3 ‐H ligands, with the four U centers arranged in a rhombic geometry. The U 4 H 8 represents not only the first example of planar polynuclear actinide metal hydride cluster but also the uranium hydride cluster with the highest nuclearity reported to date.