Octahedral cluster

Octahedral clusters are inorganic or organometallic cluster compounds composed of six metals in an octahedral array.^[1] Many types of compounds are known, but all are synthetic.

Octahedral chalcogenide and halide clusters

These compounds are bound together by metal-metal bonding as well as two kinds of ligands. Ligands that span the faces or edges of the M₆ core are labeled L_i, for inner (innen in the original German description), and those ligands attached only to one metal are labeled outer, or L_a for ausser.^[2] Typically, the outer ligands can be exchanged whereas the bridging ligands are more inert toward substitution.

Face-capped halide clusters

The premier example is of the class is Mo₆Cl₁₄²⁻. This dianion is available as a variety of salts by treating the polymer molybdenum(II) chloride with sources of chloride, even hydrochloric acid. A related example is W₆I₁₄²⁻ anion, which is obtained by reaction of tungsten hexacarbonyl with iodine at elevated temperatures.

Structure of [Mo₆Cl₁₄]²⁻, a prototypical octahedral cluster.

Chalcohalide clusters

A related class of octahedral clusters are of the type M₆X₈L₆ where M is a metal usually of group 6 or group 7, X is a ligand and more specifically an inner ligand of the chalcohalide group such as chloride or sulfide and L is an "outer ligand." The metal atoms define the vertices of an octahedron. The overall point group symmetry is O_h. Each face of the octahedron is capped with a chalcohalide and eight such atoms are at the corners of a cube. For this reason this geometry is called a face capped octahedral cluster. Examples of this type of clusters are the Re₆S₈Cl₆⁴⁻ anion

Chevrel clusters

A well-studied class of solid-state compounds related to the chalcohalides are molybdenum clusters of the type A_xMo₆X₈ with X sulfur or selenium and A_x an interstitial atom such as Pb. These materials, called Chevrel phases or Chevrel clusters, have been actively studied because they are type II superconductors with relatively high critical fields.^[3] Such materials are prepared by high temperature (1100 °C) reactions of the chalcogen and Mo metal. Structurally related, soluble analogues have been prepared, e.g., Mo₆S₈(PEt₃)₆.^[4]

Edge-Capped Halide Clusters

With metals in group 4 or 5 a so-called edge-capped octahedral clusters are more common. Twelve halides are located along the edge of the octahedron and six are terminal. Example of this type of species are the anion Ta₆Cl₁₈⁴⁻.,^[5] Nb₆F₁₅ or the Nb₆F₁₈²⁻ anion.^[1]

Structure of edge-capped octahedral clusters such as Ta₆Cl₁₈⁴⁻.

Many of the early metal clusters can only be prepared when they incorporate intertitial atoms. One example is Zr₆CCl₁₂.^[2]

Electron counting in octahedral halide and chalcogenide clusters

The species Mo₆Cl₁₄²⁻ feature Mo(II) (d⁴) centers. Six Mo(II) centers gives rise to a total of 24 valence electrons, or 2e/Mo-Mo vector. More electron-deficient derivatives such as Ta₆Cl₁₈⁴⁻ have fewer d-electrons. For example, the naked cluster Ta₆¹⁴⁺, the core of Ta₆Cl₁₈⁴⁻ would have 5(6) - 14 = 16 valence electrons. Fewer d-electrons result in weakened M-M bonding and the extended Ta---Ta distances accommodate doubly bridging halides.

Other classes of octahedral clusters

In the area of metal carbonyl clusters, a prototypical octahedral cluster is [Fe₆C(CO)₁₆]²⁻, which is obtained by heating iron pentacarbonyl with sodium. Some of the CO ligands are bridging and many are terminal. A carbide ligand resides at the center of the cluster. A variety of analogous compounds have been reported where some or all of the Fe centres are replaced by Ru, Mn and other metals.

Outside of carbonyl clusters, gold forms octahedral clusters.

The complex [Au₆C(PPh₃)₆]²⁺, containing a carbon-gold core.

References

1. Eric J. Welch and Jeffrey R. Long Atomlike Building Units of Adjustable Character: Solid-State and Solution Routes to Manipulating Hexanuclear Transition Metal Chalcohalide Clusters in Progress in Inorganic Chemistry, Volume 54 Kenneth D. Karlin ISBN 0-471-72348-7 2005 Link
2. Arndt Simon "Metal clusters inside out" Phil. Trans. R. Soc. A 2010 vol. 368, 1285-1299. doi:10.1098/rsta.2009.0271
3. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
4. Saito, T. and Imoto, H., "Chalcogenide Cluster Complexes of Chromium, Molybdenum, Tungsten, and Rhenium", Bulletin Chemical Society of Japan, 1996, volume 69, pp. 2403-2417. doi:10.1246/bcsj.69.2403
5. Koknat, F. W.; Marko, D. J. "Tetradecachlorohexatantalum Octahydrate, Ta₆Cl₁₄^.8H₂O" Inorganic Syntheses, 2004, volume 34, pp. 187-191. ISBN 0-471-64750-0. (describes Na₄Ta₆Cl₁₈)