Abstract
Kinetics results concerning nucleophilic substitutions of chloride from the complexes [Pt(bipy)(am)Cl]BPh 4 (bipy = α,α′-dipyridyl; am = ethanolamine and ethylamine) in methanol and acetonitrile are reported. The second-order kinetic rate constants together with the solubilities of the reactants provide a basis for the calculation of the transfer chemical potentials for initial and transition state of every reported reaction. The kinetic behaviour of the two complexes is very similar in methanol, but in acetonitrile the ethanolamine derivative reacts about 2–3 times faster than the ethylamine derivative. This difference is interpreted on the basis of a solvent-controlled anchimeric assistance which is provided to the leaving chloride by the dangling hydroxoresidue of the ethanolamine only in the aprotic acetonitrile.
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