Chemistry of [Fe6S6]3+ prismatic Cages. Synthesis, structural characterization, and electronic structures of the [Et4N]3[Fe6S6L6] Clusters (L = p-CH3C6H4O-, Br-)

Mercouri G Kanatzidis, A. Salifoglou, D. Coucouvanis

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Abstract

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-CH3C 6H4O)6] (I) and of [Et4N]3[Fe6S6Br 6]·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
Pages (from-to)2460-2468
Number of pages9
JournalInorganic Chemistry
Volume25
Issue number14
Publication statusPublished - 1986

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Electronic structure
chemistry
electronic structure
Atoms
Diffractometers
Sulfides
synthesis
Molecular structure
Cyclic voltammetry
Anions
Crystal structure
Nuclear magnetic resonance
Ligands
cells
diffractometers
Molecules
atoms
sulfides
molecular structure

ASJC Scopus subject areas

  • Inorganic Chemistry

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@article{c34189dd07ef4973a9b1080f3119e081,
title = "Chemistry of [Fe6S6]3+ prismatic Cages. Synthesis, structural characterization, and electronic structures of the [Et4N]3[Fe6S6L6] Clusters (L = p-CH3C6H4O-, Br-)",
abstract = "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-CH3C 6H4O)6] (I) and of [Et4N]3[Fe6S6Br 6]·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) {\AA}, b = 19.848 (10) {\AA}, c = 14.304 (4) {\AA}, and β = 98.05 (3)°. In II, a = 14.531 (3) {\AA}, b = 11.028 (2) {\AA}, c = 17.566 (3) {\AA}, 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) {\AA} and 3.80 (4), 3.81 (2) {\AA}, 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) {\AA}. The Fe-O bond in I is 1.880 (11) {\AA}, and the Fe-Br bond in II is 2.366 (9) {\AA}. The reactivity, cyclic voltammetry, and isotropically shifted NMR spectra of I and II are discussed in detail.",
author = "Kanatzidis, {Mercouri G} and A. Salifoglou and D. Coucouvanis",
year = "1986",
language = "English",
volume = "25",
pages = "2460--2468",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "14",

}

TY - JOUR

T1 - Chemistry of [Fe6S6]3+ prismatic Cages. Synthesis, structural characterization, and electronic structures of the [Et4N]3[Fe6S6L6] Clusters (L = p-CH3C6H4O-, Br-)

AU - Kanatzidis, Mercouri G

AU - Salifoglou, A.

AU - Coucouvanis, D.

PY - 1986

Y1 - 1986

N2 - 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-CH3C 6H4O)6] (I) and of [Et4N]3[Fe6S6Br 6]·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.

AB - 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-CH3C 6H4O)6] (I) and of [Et4N]3[Fe6S6Br 6]·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.

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VL - 25

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EP - 2468

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

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