Persistence of Optical Activity in an Oxidation-Reduction Reaction

Abstract

TRIS-O,PHENANTHROLINE rutheniumII perchlorate dihydrate1, Ru(phenan)3(ClO4)2.2H2O, has been resolved through the antimonyl tartarate to give [α]D20 = + 979° and – 971° and [α]546·120 = + 1869° and – 1863° for the ion Ru(phenan)3++. Burstall2 found [α]579·125 = + 860° and – 815° for the compound Ru(dipy)3I2.2H2O. The orange-red active perchlorates in 6 normal sulphuric acid were oxidized with cerie nitrate to yield the optically active blue ion Ru(phenan)3+++, for which [α]D20 = + 311° and – 303° and [α]546·120 = + 1,246° and –1,256°. Reduction of the unstable oxidized ion with ferrous sulphate regenerated the rutheniumnII complex with its rotation unchanged. It is evident that both the di- and tri-valent ruthenium complexes have a very large abnormal rotatory dispersion.

References

  1. 1

    Dwyer, Humpoletz and Nyholm, J. Proc. Roy. Soc., N.S.W., 80, 212 (1947).

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  2. 2

    Burstall, J. Chem. Soc., 172 (1936).

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DWYER, F., GYARFAS, E. Persistence of Optical Activity in an Oxidation-Reduction Reaction. Nature 163, 918 (1949). https://doi.org/10.1038/163918b0

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