Abstract
From the system of isomeric complex ions [Os(NCS)n(SCN)6-n]3-, 9 of 10 possible species, n = 1-6, are isolated, including for n = 2, 3, 4 the first representatives of pure geometric bond isomers. By reaction of K2[OsCl6] with aqueous KSCN solution at reflux temperature, trans(mer)-complexes, and on treatment at 60 °C exclusively cis(fac)- complexes are formed. By ion exchange chromatography on diethylaminoethyl-cellulose columns, from mixtures of pairs of geometric isomers the pure trans(mer)-compounds are enriched in front, the cis(fac)-species at the end of the zones. Characterization and assignment of the configuration of the geometric isomers is based upon the reproducible differences in the IR and Raman spectra.

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