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Fifteen-Tin Clusters

Largest tin clusters may pave way to broader range of metalloid nanoparticles

by Stephen K. Ritter
June 26, 2006 | A version of this story appeared in Volume 84, Issue 26

Synthesis of novel tin cluster compounds has expanded the number of tin atoms in an isolable cluster from 10 to 15 atoms, signaling a potential leap forward in the quest to controllably synthesize "metalloid" nanoparticles (Angew. Chem. Int. Ed. 2006, 45, 4333).

Metalloid clusters, of interest for their electronic properties, are defined as molecules having more metal-metal bonds than metal-ligand bonds and, given enough metal atoms, taking on the close-packed lattice structure of bulk metals. Until now, this type of molecular cluster has been known only for group 13 elements aluminum and gallium and a few precious metals such as palladium and gold.

An international research team led by Michael F. Lappert at the University of Sussex, in England, now reports the first metalloid tin clusters with the synthesis of Sn15L6, where L is a bulky amido ligand. The clusters, made by reacting a tin dimer (LSnCl2SnL) with a lithium reagent, have a central tin atom surrounded by eight tin atoms in a body-centered cubic arrangement, with the remaining six tin atoms substituted with the ligands lying outside the periphery of the cube.

Tin clusters previously had been limited to ligand-free anions, such as Sn93-, and clusters up to 10 metal atoms with ligands, such as Sn10L3-, where L is a bulky aryl group. Although tin clusters would need to have many more metal atoms to be functional nanoparticles, the ability to make the Sn15L6 clusters suggests that tin molecular nanoparticles are possibly within reach, notes team member Philip P. Power of the University of California, Davis.

The Sn15L6 clusters "are exciting new gems" for metalloid cluster chemistry, comments Slavi C. Sevov of the University of Notre Dame, whose group is working on related bimetallic metalloid clusters. "This is a very important discovery for showing that main-group metalloid clusters are not unique to one group of the periodic table."



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