Chemistry of [Fe6S6]3+ Prismatic Cages. Synthesis, Structural Characterization, and Electronic Structures of the [Et4N]3[Fe6S6L6] Clusters (L = p-CH3C6H4O-, Br-)

M. G. Kanatzidis, A. Salifoglou, D. Coucouvanis

Research output: Contribution to journalArticlepeer-review

52 Scopus citations


The syntheses of the [Cat]3[Fe6S6L6] clusters (L = Br-, cat = [Et3MeN]+; L = ArS-, Cat = [Et4N]+) are reported. The crystal and molecular structures of [Et4N]3[Fe6S6(p-CH3C6H4O)6] (I) and of [Et4N]3[Fe6S6Br6].CH3CN (II) are described in detail. I and II crystallize in the monoclinic space groups P21/a and P21/n, respectively, with two molecules in the unit cell. The cell dimensions in I are a = 13.173 (5) Å, b = 19.848 (10) Å, c = 14, 304 (4) Å, and β = 98.05 (3)°. In II, a = 14.531 (3) Å, b = 11.028 (2) Å, c = 17.566 (3) Å, and β = 100.69 (1)°. Intensity data for both I and II were collected with a four-circle computer-controlled diffractometer with use of the θ–2θ scan technique. Both structures were solved by conventional methods from 3461 and 2516 reflections for I and II, respectively. The structures were refined by full-matrix least-squares techniques (283 parameters for I and 213 parameters for II) to final R values of 0.075 and 0.049, respectively, for I and II. The anions in I and II contain the [Fe6S6]3+ hexagonal-prismatic core, which consists of alternating tetrahedral Fe and triply bridging S atoms. Three of the Fe coordination sites are occupied by core sulfide atoms while the fourth coordination site is filled by the terminal RO-and Br-ligands. There are two sets of Fe. Fe distances in the Fe6S6 cores with mean values of 2.761 (5), 2.749 (4) Å and 3.80 (4), 3.81 (2) Å, respectively, for I and II. Similarly, two sets of Fe-S-Fe angles are found for I and II at 74.6 (2) and 74.3 (1)° and 113.8 (2) and 114.2 (9)°. The Fe-S* bonds in I and II are 2.276 (5) and 2.274 (4) Å. The Fe-O* bond in I is 1.880 (11) Å, and the Fe-Br bond in II is 2.366 (9) Å. The reactivity, cyclic voltammetry, and isotropically shifted NMR spectra of I and II are discussed in detail.

Original languageEnglish (US)
Pages (from-to)2460-2468
Number of pages9
JournalInorganic chemistry
Issue number14
StatePublished - Jul 1986

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Chemistry of [Fe<sub>6</sub>S<sub>6</sub>]<sup>3+</sup> Prismatic Cages. Synthesis, Structural Characterization, and Electronic Structures of the [Et<sub>4</sub>N]<sub>3</sub>[Fe<sub>6</sub>S<sub>6</sub>L<sub>6</sub>] Clusters (L = p-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>O<sup>-</sup>, Br<sup>-</sup>)'. Together they form a unique fingerprint.

Cite this