Summary
Kinetics of formation of [PdCl4]2− from [Pd(ox)2]2− and [Pd(mal)2]2− has been studies in aqueous acid media in the presence of an excess of chloride ion by stopped-flow spectrophotometry. Both the complexes undergo the transformation in two well separated consecutive steps. In 0.02–0.05 M acid with 0.2 M Cl−, Pd(AA)2− dissociates leading to the formation of [Pd(AA)Cl2]2− (where AA =ox2− or mal2−), which in 0.1–0.6 M acid and 1 M Cl− forms [PdCl4]2− in a relatively slow step. For both steps kabs=k0+k2[H+][Cl−]. Activation parameters corresponding to k0 and k2 have been determined. Results indicate that [Pd(mal)2]2− is much more labile to substitution than [Pd(ox)2]2− and for both the lability is far greater than that of [Pd(bigH)2]2+ and [Pt(ox)2]2− reported earlier.
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Das, A.K., Gangopadhyay, S. & Banerjea, D. Kinetics and mechanism of formation of tetrachloropalladate(II) in the reactions of bis(oxalato)- and bis(malonato) palladate(II) with chloride in acid media. Transition Met Chem 14, 73–75 (1989). https://doi.org/10.1007/BF01129765
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DOI: https://doi.org/10.1007/BF01129765