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Niobium and Tantalum Halocyanide Clusters: The Complete Family
Maxim Shamshurin1, Artem Gushchin1, Sergey Adonin1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Prospekt Lavrentyeva 3, 630090 Novosibirsk, Russian Federation.
Abstract:
Synthetic procedures providing straightforward access to the whole family of Nb and Ta halide clusters with terminal cyanide ligands have been developed. Corresponding [M6X12(CN)12]4- (M = Nb, Ta; X = Cl, Br) can be accessed by ligand-exchange procedures from K4Nb6X18 (X = Cl, Br) and Bu4NCN, (Et4N)2[Ta6Cl18] and Bu4NCN and from [Ta6Br12(H2O)4Br2]·4H2O and KCN in moderate to high yields (50-80%). The products were isolated as Bu4N salts. The compounds were investigated both experimentally and by quantum chemistry, revealing correlations between structural, electrochemical, electrostatic, electronic, and topological features as a function of type of metal, halide, and charge.
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