Reactions of oxygenated cobalt (II) complexes. XIII. Diastereoisomeric forms of μ-peroxo-μ-hydroxo-bis[bis(ethylenediamine) cobalt(III)]. Preparation, X-ray structure determination and reactivity
✍ Scribed by Silvio Fallab; Margareta Zehnder; Ulf Thewalt
- Publisher
- John Wiley and Sons
- Year
- 1980
- Tongue
- German
- Weight
- 413 KB
- Volume
- 63
- Category
- Article
- ISSN
- 0018-019X
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✦ Synopsis
Abstract
Oxygenation of solutions containing bis(ethylenediamine) cobalt(II) ions leads to a mixture of diastereomeric forms of μ‐peroxo‐μ‐hydroxo‐bis[bis(ethylenediamine) cobalt(III)] cations. The existence of a meso‐isomer has now been proved by its isolation as perchlorate and by an X‐ray structure determination. The crystals are monoclinic with space group P2~1~/n and lattice constants: a = 19.280, b = 11.984, c = 11.654 Å, β = 99.190°.
The UV./VIS. spectra of the isomers are practically identical but show different kinetic behaviour. In acidic solution the meso‐isomer decomposes 4 times faster than the racemic form. In alkaline solution the meso‐isomer isomerizes to the racemic form. A mechanism which explains all the kinetic observations has been devised.