Octahedral {Ta6I12} Clusters

Maxim V. Shamshurin, Maxim A. Mikhaylov, Taisia Sukhikh, Enrico Benassi, Alexandra R. Tarkova, Alexey A. Prokhorikhin, Evgeniy I. Kretov, Michael A. Shestopalov, Pavel A. Abramov, Maxim N. Sokolov

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

Ta powder reacts with I2 at 650 °C with the formation of Ta6I14, which belongs to the family of {M6(μ-X)12} clusters. It undergoes aquation with the formation of the intensely colored [Ta6I12(H2O)6]2+. The crystal structure was determined for [Ta6I12(H2O)6](BPh4)2·xH2O (Ta-Ta 2.9322(6) Å, Ta-I 2.8104(7) Å, Ta-O 2.3430(5) Å). With DMF, [Ta6I12(DMF)6]I2·xDMF was isolated (Ta-Ta 2.9500(2) Å, Ta-I 2.8310(4) Å, Ta-O 2.2880(7) Å). Cyclic voltammetry of [Ta6I12(H2O)6]2+ shows two consecutive quasi-reversible one-electron oxidations (E1/2 0.61 and 0.92 V vs Ag/AgCl). Reaction of Ta6I14 with Bu4NCN yields (Bu4N)4[Ta6I12(CN)6]·xCH3CN (Ta-Ta 2.9777(4) Å, Ta-I 2.8165(6) Å, Ta-C 2.2730(7) Å). Quantum chemical calculations reproduce well the experimental geometry of the aqua complex and show the essentially Ta-centered nature of both the HOMO and LUMO. The long-term stability of [Ta6I12(H2O)6]2+ solutions can be greatly enhanced in the presence of polystyrenesulfonate (PSS), which forms nanoparticle associates with the aqua complex in water (ca. 1 cluster per 3 PSS monomeric units).

Original languageEnglish
Pages (from-to)9028-9035
Number of pages8
JournalInorganic Chemistry
Volume58
Issue number14
DOIs
Publication statusPublished - 24 Jun 2019

Keywords

  • MAGNETIC-PROPERTIES
  • BASIS-SETS
  • HEXANUCLEAR
  • NIOBIUM
  • TANTALUM
  • HALIDE
  • COMPLEXES
  • THERMOCHEMISTRY
  • SPECTRA
  • VALENCE

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