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.2010 Mar 28;368(1915):1265-84.
doi: 10.1098/rsta.2009.0270.

Polyhedral nine-atom clusters of tetrel elements and intermetalloid derivatives

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Polyhedral nine-atom clusters of tetrel elements and intermetalloid derivatives

Sandra Scharfe et al. Philos Trans A Math Phys Eng Sci..

Abstract

Homoatomic polyanions have the basic capability for a bottom-up synthesis of nanostructured materials. Therefore, the chemistry and the structures of polyhedral nine-atom clusters of tetrel elements [E(9)](4-) is highlighted. The nine-atom Zintl ions are available in good quantities for E = Si-Pb as binary alkali metal (A) phases of the composition A(4)E(9) or A(12)E(17). Dissolution or extraction of the neat solids with aprotic solvents and crystallization with alkali metal-sequestering molecules or crown ethers leads to a large variety of structures containing homoatomic clusters with up to 45 E atoms. Cluster growth occurs via oxidative coupling reactions. The clusters can further act as a donor ligand in transition metal complexes, which is a first step to the formation of bimetallic clusters. The structures and some nuclear magnetic resonance spectroscopic properties of these so-called intermetalloid clusters are reviewed, with special emphasis on tetrel clusters that are endohedrally filled with transition metal atoms.

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