Issue 8, 1993

Kinetics of the reaction of dichloro-trans-rac- and -cis-meso-1,2-diaminocyclohexaneplatinum(II) with pyridine

Abstract

The kinetics of the reaction [Pt(dach)Cl2]+ py →[Pt(dach)(py)Cl]Cl (dach = either trans-rac- or cis-meso-1,2-diaminocyclohexane, py = pyridine) has been studied in dimethylformamide (dmf) solution, under pseudo-first-order conditions (excess of pyridine), in the range 50–80 °C, by measuring the increase in conductance of the solution. In dmf the products behave like weak electrolytes, with dissociation constants of about 1.4 × 10–3 mol dm–3. The reactions were found to be reversible under the experimental conditions. Owing to the uncertainty in evaluating the equilibrium concentrations, the kinetic constants kobs have been calculated from the initial slopes (up to 15% conversion) of first-order plots. Their values obey the equation kobs=k1+k2[py], k1 being about two orders of magnitude lower than k2. The values of kobs for the cis derivative are always slightly but significantly higher than those of the trans. The activation parameters have been evaluated only for k2, since the k1 values are affected by too high uncertainties: ΔHtrans 76(1), cis 79(1) kJ mol–1; ΔStrans–101(3), cis–92(3) J K–1 mol–1. The higher rate for the cis isomer is interpreted in terms of higher flexibility of the diamine chelate ring.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1993, 1231-1235

Kinetics of the reaction of dichloro-trans-rac- and -cis-meso-1,2-diaminocyclohexaneplatinum(II) with pyridine

G. D'Alfonso and A. Pasini, J. Chem. Soc., Dalton Trans., 1993, 1231 DOI: 10.1039/DT9930001231

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