Pressure dependencies of
the nucleophile-independent rate constants were studied for the reactions of
[Pd(teden)X]n+ ions (where teden = N'-[2-(diethylamino)ethyl]-N,N-diethylethane-1,2-diamine and X = Cl-,
Br-, N3-, I-, SCN- and
NH3) with various nucleophiles, Y. The partial molar volumes of
these complexes were measured at 25�C. By combining these values with the
respective volumes of activation, volume profile diagrams were constructed from
which the reaction mechanism was determined to be of the interchange type, most
likely Ia.
For three representative reactions, in which X = Cl-
and Br-, and Y = N3- and SCN-, ΔV‡exp
values for the nucleophile-dependent path were also derived. The mechanism of
these reactions is also considered to be concerted.