Synthesis, structures, and properties of new chalcogenide-capped octahedral hexatechnetium(III) complexes [Tc6S8X6] 4- (X = Br, I), [Tc6Se8I2], and [Tc6Te15]

Takashi Yoshimura, Ikai TakuyaM, Yuji Tooyama, Tsutomu Takayama, Tsutomu Sekine, Yasushi Kino, Akira Kirishima, Nobuaki Sato, Toshiaki Mitsugashira, Naruto Takahashi, Atsushi Shinohara

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

Chalcogenide-capped octahedral hexatechnetium(III) complexes, Cs 4[Tc6S8Br6]·CsBr (Cs 4[1]·CsBr) and (PPh4)4[Tc 6S8Br6] {(PPh4)4[1]}, (PPh4)4[Tc6S8I6] ((PPh4)4[2]}, [Tc6Se8I2] ([3]), and [Tc6Te15] ([4]) were synthesized. Single-crystal X-ray structural studies were carried out for Cs 4[1]·CsBr, [3], and [4], Sulfide-capped octahedral hexatechnetium(III) clusters [1]4- and. [2]4- are discrete complex anions, whereas the selenideand telluride-capped hexatechnetium(III) complexes adopt extended polymeric structures. A cyclic voltammogram of [1] 4- in CH3CN showed two one-electron redox waves: Tc 6(24e/23e) and Tc6(23e/22e). The potential of the Tc 6(24e/ 23e) process is more positive than that of the Re 6(24e/23e) process for the hexarhenium analog [Re6S 8X6]4- (X = Br, I), whereas that of the Tc 6(23e/22e) process shifts to negative values compared, to the potential, of the Re6(23e/22e) process. Thus, the Tc6(23e) mixed-valence state is thermodynamically less stable than Re6(23e).

Original languageEnglish
Pages (from-to)1214-1219
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Issue number8
DOIs
Publication statusPublished - 2010

Keywords

  • Chalcogens
  • Cluster compounds
  • Cyclic voltammetry
  • Technetium

ASJC Scopus subject areas

  • Inorganic Chemistry

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