| Synthesis of New Cluster Cores |
| Low-temperature
solid-state conditions have permitted high-yield syntheses of
new cluster cores with interesting structures.
Further exploration could greatly enhance the library of
hexanuclear clusters. A trigonal-prismatic
hexanuclear tungsten-chloride cluster,
centered by a carbon atom, has been prepared by the reaction: 6 WCl6 + CCl4 + 8 Bi → [W6CCl18]2- + 8
BiCl3 The
cluster exhibits rich electrochemistry for a
cluster of its type and several oxidation states have been
isolated. It is expected that this new structure type is general
and a nitrogen-centered analogue has also been characterized.
Replacement of the terminal chloride ligands with bridging ligands,
such as cyanides, may allow incorporation of the cluster into
magnetic porous frameworks with non-cubic geometries. |
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