Hexol

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Hexol
Hexol-2D-wedged.png
Hexol-cation-from-xtal-2000-3D-balls.png
Properties
Molecular formulaH42Co4N12O18S3
Molar mass830.33 g mol−1
Solubility in waterSparingly soluble in water [1]
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references
 
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Hexol
Hexol-2D-wedged.png
Hexol-cation-from-xtal-2000-3D-balls.png
Properties
Molecular formulaH42Co4N12O18S3
Molar mass830.33 g mol−1
Solubility in waterSparingly soluble in water [1]
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY (verify) (what is: YesY/N?)
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[edit]

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[edit]

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"[edit]

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]

Werner's second hexol 2004 interpretation

References[edit]

  1. ^ a b 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[edit]