Rates and mechanisms of substitution reactions of square-planar dithiocarbamate and dithiophosphate complexes of the nickel triad in methanol
Abstract
Rate constants for the substitution reactions of square-planar dithiophosphate and dithiocarbamate complexes of NiII, PdII, and PtII, with ethylenediamine and cyanide ion as nucleophiles, have been measured in methanol at an ionic strength of 0.1 mol dm–3 sodium perchlorate. A general mechanism is proposed to account for the kinetic data. The order of the reactivity of the complexes is approximately Ni : Pd : Pt = 105 : 103 : 1. The results are compared with those obtained in previous investigations and are interpreted in terms of the stabilities of the five-co- ordinate species which are formed prior to substitution.