Can M6X8 clusters form intercluster metal metal bonds?
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M6X8 clusters are always found to form exo bonds to donor ligands. This behavior is simply understood in terms of the electronic structure of the cluster core: the LUMO orbitals of the clusters have a σ-acceptor character. These relatively low-lying orbitals should be available for intercluster metal-metal bond formation providing species can be made that have a formal cluster d-electron count greater than 24. Cluster dimers should be stable for 25 electrons per cluster, and 26 electrons per cluster is favorable for one-dimensional polymers. A cubic “Chevrel phase alternative” structure utilizing M608 clusters is promising in that the steric requirements of the oxo clusters allow the tight packing necessary for intercluster metal-metal bonding. A sampling of molecules and extended systems is treated, and analogies are drawn with known or potential B6 species. © 1986, American Chemical Society. All rights reserved.
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