10.1002/anie.201812509
Angewandte Chemie International Edition
COMMUNICATION
were isolated from colloidal solutions of plutonium.[2e, 6g] While the
assignment of the composition and uranium charge remained
ambiguous in the previously reported [U38O56Cl18] cluster, the
composition and the uranium oxidation state (+IV) are non-
ambiguous in 7.Due to the very low yield in 7 and to the presence
of multiple products further characterization of this cluster was not
possible. From a comparison of the structure of {U24} and {U38} it
can be clearly seen that the latter builds up from the first through
the deprotonation of two hydroxo ligands still present in the {U24}
cluster. Attempts to build {U38} from {U24} by using different bases
have not been yet successful but should provide a more
convenient route to {U38}.
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U13
[3]
U24
U16
U10
U6
base
0
2
Time/days
2
21
UCl4
CH3CN/2H2O
+
Time/days
X=2
X KL
Ligand/U ratio
[4]
+ UO2
U38
X= 3-6
25
Temperature/°C
80
[5]
[6]
U6 (Flat)
Figure 6. Assembly pathway of uranium oxo/hydroxo clusters in the controlled
hydrolysis of UCl4 in presence of the benzoate ligand.
In summary (Figure 6) during the hydrolysis of UCl4 in presence
of the benzoate ligand in coordinating solvents (pyridine), the
formation of the hexanuclear [U6O4(OH)4] cluster occurs rapidly
and formation of larger assembly is not observed. In contrast the
hexanuclear clusters assemble slowly in acetonitrile solution,
probably via oxolation condensation reactions, leading to a
mixture of {U10} and {U13} clusters. The addition of base to these
clusters promotes further condensation affording a {U16} cluster
with a [U16O15(OH)8] core. Both the {U16} and {U13} can further
slowly assemble with additional {U13} and/or {U6} units to yield a
{U24} cluster with a [U24O30(OH)2] core. When the reaction of
hydrolysis is carried at higher temperature small amounts of a
{U38} cluster with a [U38O56] core, were isolated. The {U38} cluster
most likely is formed by the condensation of two {U24} clusters and
two additional {U6} units prior to the formation of the final UO2
product. In conclusion the controlled hydrolysis of uranium(IV)
complexes in organic solvents provides an attractive route to the
synthesis of uranium clusters with diverse structure and nuclearity.
Moreover, it provides insightful snapshots of the time-dependent
assembly pathway from uranium hexamers to larger oligomeric
species. These results pave the way to the further development
of the cluster chemistry of low valent actinides.
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Acknowledgements
We thank E. Solari for elemental analysis. This work was
supported by the Ecole Polytechnique Fédérale de Lausanne
(EPFL) and by the Swiss National Science Foundation grant
(number CR23I2_16645).
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Keywords: cluster compounds• uranium • actinides • self-
assembly • polyoxometalates
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