Reduction of OsO4by some imidazolidine-2-thiones. X-ray crystal structure of trans- dichlorotetrakis(NN′-diethylimidazolidine-2-thione)osmium(IV) diperchlorate
- 1 January 1983
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 7,p. 1261-1264
- https://doi.org/10.1039/dt9830001261
Abstract
Osmium tetroxide is reduced to an OsIII complex by reaction with some N-monosubstituted Imidazolidine-2-thiones in H2O–EtOH in the presence of HClO4. In order to clarify the mechanism of this reduction, NN′-dimethyl- and NN′-diethyl-Imidazolidine-2-thiones (L), with low reducing power, were employed. Intermediate species of OsVI and OsIV with formulae [OsO2L4][ClO4]2 and [OsCl2L4][ClO4]2 were isolated. The title compound crystallizes in the triclinic space group P with unit-cell dimensions a= 11.845(2), b= 10.451(2), c= 9.376(3)Å, α= 70.659(9), β= 86.670(9), γ= 86.708(5)°, and z= 1. The structure was solved by the heavy-atom method and refined by least-squares calculations to a conventional R factor of 0.023 for 4 087 counter data. It consists of discrete trans-dichlorotetrakis(NN′-dimethylimidazolidine-2-thione)osmium(IV) dications, in which the metal atom is bonded in a nearly idealized octahedral geometry to four S and two trans CI atoms, and of disordered C1O4 – anions. The i.r.-active vasym.(OsCI2) is assigned at ca. 300 cm–1 for the [OsC12L4][ClO4]2 complexes.Keywords
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