Niobium and Tantalum Halocyanide Clusters: The Complete Family

Maxim Shamshurin; Artem Gushchin; Sergey Adonin; Enrico Benassi; Maxim Sokolov

doi:10.1021/acs.inorgchem.2c01824

Niobium and Tantalum Halocyanide Clusters: The Complete Family

Inorg Chem. 2022 Oct 24;61(42):16586-16595. doi: 10.1021/acs.inorgchem.2c01824. Epub 2022 Sep 26.

Authors

Maxim Shamshurin¹, Artem Gushchin¹, Sergey Adonin¹, Enrico Benassi², Maxim Sokolov^{1

2}

Affiliations

¹ Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Prospekt Lavrentyeva 3, 630090 Novosibirsk, Russian Federation.
² Novosibirsk State University, Ulitsa Pirogova 2, 630090 Novosibirsk, Russian Federation.

PMID: 36162107
DOI: 10.1021/acs.inorgchem.2c01824

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.