Reducing Nitrogen

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Science  04 Mar 2005:
Vol. 307, Issue 5714, pp. 1377
DOI: 10.1126/science.307.5714.1377a

The formation of stable and well-defined inorganic clusters often requires the presence of chelating organic ligands. Rather et al. report using an organic reaction to drive the formation of a hydroxyl-bridged Ga13 cluster. The oxidation of nitrosobenzene to nitrobenzene can be coupled to the reduction of nitrate, and using Ga(NO3)3 as the source of nitrate yields as a product the compound [Ga133-OH)62-OH)18(H2O)24](NO3)15, in which the N: Ga stoichiometry has been reduced from 3:1 to 15:13. Unlike related Al13 clusters, which have a modified Keggin ion structure, x-ray crystallography reveals that the Ga13 cluster is similar to ligand-stabilized clusters in that it has an octahedral Ga core, which is bridged by hydroxyl groups to six Ga cations that are, in turn, surrounded by six hydrated Ga ions. All together, this cluster forms a disklike structure about 1 nm thick and about 2 nm in diameter. — PDS

J. Am. Chem. Soc. 10.1021/ja043520t (2005).

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