Kinetics and mechanism of formation of tetrachloropalladate(II) in the reactions of bis(oxalato)- and bis(malonato) palladate(II) with chloride in acid media |
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| Authors: | Asim Kumar Das Soma Gangopadhyay Debabrata Banerjea |
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| Affiliation: | (1) Inorganic Chemistry Division, Department of Chemistry, University College of Science, 92 Acharya Prafulla Chandra Road, 700 009 Calcutta, India |
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| Abstract: | 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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