Abstract
The kinetics of the substitution reactions of the protonated froms oftrans-tetracyanodioxorthenate(V) with thiourea (TU),N-methylthiourea (NMTU),N, N′-dimethylthiourea (NNDMTU) and hydrazoic acid (HN3) were studied. The results were compared with those obtained for similar reactions of [WO2(CN)4]4−. This study showed that the diprotonated form [ReO(H2O)(CN)4]− is the only species reactive towards substitution reactions (and not the [ReO(OH)(CN)4]2− ion) and that only the aqua ligand in [ReO(H2O)(CN)4]− is substituted by the incoming group. A dissociative mechanism is proposed for the substitution reactions between [ReO(H2O)(CN)4]− and the monodentate nucleophiles. The i.r. data for these Rev complexes are reported and discussed in terms of the relativetrans influence of the various monodentate ligands.
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