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- W2008376421 abstract "Perchlorate and bromide salts of the µ-amido-µ-selenato-bis[tetra-amminecobalt(III)] complex have been prepared and characterised. Equilibrium and kinetic studies on the interconversion [equation (i)] of the µ-amido-µ-hydroxo-(I) and µ-amido-µ-selenato-complexes (III) at I= 2·0M(NaClO4) are described. [graphic omitted] From spectrophotometric studies at 25 °C, the overall equilibrium constant K12= 265 ± 5 I2 mol–2. For the forward reaction, the conversion of (I) into (II) is rate determining and first-order rate constants, kf, show the dependence kf/S–1=k1a[H+][SeO42–]. At 25 °C, k1a= 1·35 × 10–2 I2 mol–2 s–1, ΔH1a‡= 18·2 ± 0·3 kcal mol–1 and ΔS1a‡=–6·3 ± 0·9 cal K–1 mol–1. The reverse reaction shows a dependence on [H+] of the form kr/s–1=a+b[H+] over the temperature range 45–60 °C, where kr=k–2k–1/k2. At 25 °C extrapolated values of a and b are 3·85 × 10–5 s–1 and 8·6 × 10–6 l mol–1 s–1 respectively. Activation parameters are ΔHa‡= 16·4 ± 0·4 kcal mol–1, ΔSa‡=–30·2 ± 1·4 cal K–1 mol–1; and ΔHb‡= 16·4 ± 1·6 kcal mol–1 and ΔSb‡=–36·3 ± 4·6 cal K–1 mol–1." @default.
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- W2008376421 date "1973-01-01" @default.
- W2008376421 modified "2023-09-30" @default.
- W2008376421 title "Reactions of µ-hydroxo-dicobalt(III) complexes. Part IX. Equilibrium and kinetic studies of the reaction of the µ-amido-µ-hydroxo-bis[tetra-amminecobalt(III)] complex with selenate ions in aqueous perchloric acid solutions, and characterisation of the µ-amido-µ-selenato-bis[tetra-amminecobalt(III)] complex" @default.
- W2008376421 doi "https://doi.org/10.1039/dt9730000504" @default.
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