Hexol

Hexol
Names
IUPAC name
Tris[tetrammine-μ-dihydroxocobalt(III)]cobalt (III) ion
Properties
Molecular formula
 H42Co4N12O18S3
Molar mass 830.33 g·mol−1
Sparingly soluble in water [1]
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Hexol is the name for various salts of a coordination complex that has historical significance. The salts were the first synthetic non-carbon-containing chiral compounds.[2] The sulfate salt has the formula {[Co(NH3)4(OH)2]3Co}(SO4)3.

Preparation and optical resolution

Salts of hexol were first described by Jorgenson.[3] The salt is prepared by heating [Co(NH3)4(H2O)2]3+ with dilute base such as ammonia followed by precipitation of the sulfate salt:

4 [Co(NH3)4(H2O)2]3+ → {[Co(NH3)4(OH)2]3Co}6+ + 4 NH4+ + 2 H+ + 2 H2O

Depending on the conditions one obtains the 9-hydrate, the 6-hydrate, and the 4-hydrate. These salts exists as dark brownish-violet or black tabular crystals. The salts has low solubility in water. The cation can be quantitatively precipitated from its yellow-gray chromate and hexachloroplatinate salts. When treated with concentrated hydrochloric acid, hexol converts to cis-diaquotetramminecobalt(III) sulfate. In boiling dilute sulfuric acid, hexol degrades with evolution of oxygen and nitrogen.[1]

Optical resolution

In a historic set of experiments, Alfred Werner obtained chiral resolution by fractional crystallisation of the diastereomeric D-(+)-bromocamphorsulphonate salt. This ion has a high specific rotation of 2640°.[4] More efficient methods involve the bis(tartrato)diantimonate(III) salt.[5]

The "second hexol"

Werner also described a second achiral hexol (a minor byproduct from the production of Fremy's salt) that he incorrectly identified as a linear trimer. The second hexol is hexanuclear (contains six cobalt centres in each ion), not tetranuclear.[6]

References

  1. ↑ 1.0 1.1 George B. Kauffman, Robert P. Pinnell "Tris[Tetrammine-μ-Dihydroxo-Cobalt(III)] Cobalt(III) Sulfate 4-Hydrate" Inorganic Syntheses, 1960 Volume 6, pp. 176–179. doi:10.1002/9780470132371.ch56
  2. ↑ G. L. Miessler and D. A. Tarr “Inorganic Chemistry” 3rd Ed, Pearson/Prentice Hall publisher, ISBN 0-13-035471-6.
  3. ↑ S. M. Jörgensen "Zur Konstitution der Kobalt-, Chrom- und Rhodiumbasen" Zeitschrift für anorganische Chemie 1898, volume 16, pages 184–197. doi:10.1002/zaac.18980160116
  4. ↑ Werner, A. (1907). "Über mehrkernige Metallammoniake" [Poly-nucleated Metal-amines]. Ber. Dtsch. Chem. Ges. (in German) 40: 2103–2125. doi:10.1002/cber.190704002126. ISSN 0365-9496.
  5. ↑ Takaji Yasui, Tomoharu Ama, George B. Kauffman "Resolution of the Dodecaamminehexa-μ-Hydroxo-Tetracobalt(III) Ion" Inorganic Syntheses 1992, vol. 29, pp. 169–174. doi:10.1002/9780470132609.ch41.
  6. ↑ W. Gregory Jackson, Josephine A. McKeon, Margareta Zehnder, Markus Neuberger, Silvio Fallab "The rediscovery of Alfred Werner's second hexol" Chemical Communications, 2004, pp. 2322–2323. doi:10.1039/B408277J.

External links