High potential isomeric dihalobis[2-(arylazo)pyridine] osmium(III) perchlorate monohydrate
✍ Scribed by T. K. Mallick; P. K. Das; B. K. Roy; B. K. Ghosh
- Publisher
- Springer
- Year
- 1993
- Tongue
- English
- Weight
- 465 KB
- Volume
- 18
- Category
- Article
- ISSN
- 0340-4285
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✦ Synopsis
The preparation of isomeric complexes [OsIUX2L2]C104 9 H20 [(4) and(5): X = CI or Br, L(1) = 2-(phenylazo)pyridine(L 1) or 2-(m-tolylazo)pyridine(L2)] via stereoretentive oxidation of the corresponding osmium(II) precursors [( 2) and (3), respectively] is described. The complexes were characterized using spectroscopic and electrochemical methods. The low-spin (idealized t~o; S = 1/2) paramagnetic complex ions display characteristic osmium(III) e.p.r, spectra in frozen (-196 ~ C) MeCN-PhMe. In dry MeCN solution, the OsX2N 4 unit exhibits irreversible [OsXzL2]2+/[OsXzL2] + and reversible [OsX2L2] +/[-OsX2L2] couples at ca. 1.8 and 1.0 V versus saturated calomel electrode (s.c.e.), respectively. The use of (4)/( 5) as an oxidant is noted.