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Structural Snapshots of Cluster Growth from {U 6 } to {U 38 } During the Hydrolysis of UCl 4
Author(s) -
Chatelain Lucile,
Faizova Radmila,
FadaeiTirani Farzaneh,
Pécaut Jacques,
Mazzanti Marinella
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201812509
Subject(s) - uranium , cluster (spacecraft) , chemistry , hydrolysis , octahedron , crystallography , ligand (biochemistry) , condensation , stereochemistry , crystal structure , materials science , organic chemistry , physics , thermodynamics , receptor , biochemistry , computer science , programming language , metallurgy
Herein we report the assembly of large uranium(IV) clusters with novel nuclearities and/or shapes from the controlled hydrolysis of UCl 4 in organic solution and in the presence of the benzoate ligands. {U 6 }, {U 13 }, {U 16 }, {U 24 }, {U 38 } 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 {U 6 } 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 {U 6 } (few hours), {U 16 } (3 days), {U 24 } (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.