Hexol

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Hexol
Hexol-2D-wedged.png
Hexol-cation-from-xtal-2000-3D-balls.png
Names
IUPAC name
Tris[tetrammine-μ-dihydroxocobalt(III)]cobalt (III) ion
Properties
Co4H42N12O18S3
Molar mass 830.31 g·mol−1
Sparingly soluble in water [1]
Except where otherwise noted, data are 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[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-(+)-bromocamphorsulfonate 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 Kauffman, George B. and Pinnell, Robert P. (1960). "Tris[Tetrammine-μ-Dihydroxo-Cobalt(III)] Cobalt(III) Sulfate 4-Hydrate". Inorganic Syntheses 6: 176–179. doi:10.1002/9780470132371.ch56. ISBN 9780470132371. 
  2. ^ Miessler, G. L. and Tarr, D. A. Inorganic Chemistry, 3rd ed., Pearson/Prentice Hall publisher, ISBN 0-13-035471-6.
  3. ^ Jörgensen, S. M. (1898). "Zur Konstitution der Kobalt-, Chrom- und Rhodiumbasen". Zeitschrift für anorganische Chemie 16: 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 (2): 2103–2125. doi:10.1002/cber.190704002126. 
  5. ^ Yasui, Takaji; Ama, Tomoharu and Kauffman, George B. (1992). "Resolution of the Dodecaamminehexa-μ-Hydroxo-Tetracobalt(III) Ion". Inorganic Syntheses 29: 169–174. doi:10.1002/9780470132609.ch41. ISBN 9780470132609. 
  6. ^ Jackson, W. Gregory; McKeon, Josephine A.; Zehnder, Margareta; Neuberger, Markus; Fallab, Silvio (2004). "The rediscovery of Alfred Werner's second hexol". Chemical Communications (20): 2322–2323. doi:10.1039/B408277J. 

External links[edit]