Structural Snapshots of Cluster Growth from {U6 } to {U38 } During the Hydrolysis of UCl4.

Herein we report the assembly of large uranium(IV) clusters with novel nuclearities and/or shapes from the controlled hydrolysis of UCl4 in organic solution and in the presence of the benzoate ligands. {U6 }, {U13 }, {U16 }, {U24 }, {U38 } oxo and oxo/hydroxo clusters were isolated and crystallographically characterized. These structural snapshots indicate that larger clusters are slowly built from the condensation of octahedral {U6 } building blocks. The uranium/benzoate ligand ratio, the reaction temperature and the presence of base play an important role in determining the structure of the final assembly. Moreover, the isolation of different size cluster {U6 } (few hours), {U16 } (3 days), {U24 } (21 days) from the same solution in a chosen set of conditions shows that the assembly of uranium oxo clusters in hydrolytic conditions is time dependent.