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Thermodynamics for complex formation between palladium(ii) and oxalate.

Dalton transactions (Cambridge, England : 2003) (2014-06-11)
Radomír Pilný, Přemysl Lubal, Lars I Elding
ABSTRACT

Complex formation between [Pd(H2O)4](2+) and oxalate (ox = C2O4(2-)) has been studied spectrophoto-metrically in aqueous solution at variable temperature, ionic strength and pH. Thermodynamic parameters at 298.2 K and 1.00 mol dm(-3) HClO4 ionic medium for the complex formation [Pd(H2O)4](2+) + H2ox ⇄ [Pd(H2O)2(ox)] + 2H3O(+) with equilibrium constant K1,H (in mol dm(-3)) are log10K1,H = 3.38 ± 0.08, ΔH = -33 ± 3 kJ mol(-1), and ΔS = -48 ± 11 J K(-1) mol(-1), as determined from spectrophotometric equilibrium titrations at 15.0, 20.0, 25.0 and 31.0 °C. Thermodynamic overall stability constants β (in (mol dm(-3))(-n), n = 1,2) for [Pd(H2O)2(ox)] and [Pd(ox)2](2-) at zero ionic strength and 298.2 K, defined as the equilibrium constants for the reaction Pd(2+) + nox(2-) ⇄ [Pd(ox)n](2-2n) (water molecules omitted) are log10β = 9.04 ± 0.06 and log10β = 13.1 ± 0.3, respectively, calculated by use of Specific Ion Interaction Theory from spectrophotometric titrations with initial hydrogen ion concentrations of 1.00, 0.100 and 0.0100 mol dm(-3) and ionic strengths of 1.00, 2.00 or 3.00 mol dm(-3). The values derived together with literature data give estimated overall stability constants for Pd(ii) compounds such as [Pd(en)(ox)] and cis-[Pd(NH3)2Cl2], some of them analogs to Pt(ii) complexes used in cancer treatment. The palladium oxalato complexes are significantly more stable than palladium(ii) complexes with monodentate O-bonding ligands. A comparison between several different palladium complexes shows that different parameters contribute to the stability variations observed. These are discussed together with the so-called chelate effect.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Oxalic acid dihydrate, SAJ first grade, 99.0-101.0%
Sigma-Aldrich
Oxalic acid dihydrate, BioUltra, ≥99.0% (RT)
Sigma-Aldrich
Oxalic acid dihydrate, puriss. p.a., ACS reagent, reag. ISO, reag. Ph. Eur., ≥99.5% (manganometric)
Sigma-Aldrich
Oxalic acid dihydrate, ACS reagent, ≥99%
Sigma-Aldrich
Oxalic acid dihydrate, ReagentPlus®, ≥99.0% (GC)
Sigma-Aldrich
Oxalic acid dihydrate, JIS special grade, 99.5-100.2%
Sigma-Aldrich
Perchloric acid, SAJ super special grade, 60.0-62.0%
Supelco
Perchloric acid, 0.01 M HClO4 in water (0.01N), eluent for IC
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Perchloric acid, 0.1 M
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Perchloric acid, 70%, 99.999% trace metals basis
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Perchloric acid, puriss. p.a., ACS reagent, reag. ISO, reag. Ph. Eur., 70.0-72.0%
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Perchloric acid, puriss. p.a., ACS reagent, packed in coated, shock- and leak-protected glass bottle, ≥60% (T)
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