Abstract
The pressure dependencies of the rates of solvolysis of [Pd(Et 4dien)I] + in the presence of 0.05 M Br − were measured in methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide and acetonitrile at 40 °C. The respective volumes of activation are −13.4 ± 0.5, −12.9 ± 0.4, −10.1 ± 0.2, −9.3 ± 0.3 and −7.9 ± 0.5 cm 3 mol −1. The temperature depen- dencies of the rate constants were also determined for the solvents acetonitrile, acetone and N,N- dimethylacetamide to supplement the existing data in the remaining solvents. An associative interchange mechanism is favored to explain these results.
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