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- W2103138026 abstract "Abstract The kinetics of oxidation of [Cr III cdta(H 2 O)] − and [Cr III dtpa(H 2 O)] 2− (where cdta = trans ‐1,2‐diaminocyclohexane‐ N , N , N ′, N ′‐tetraacetate and dtpa = diethylenetriaminepentaacetate) by periodate ion has been studied in aqueous solutions. The oxidation of these complexes was carried out in the pH range 5.52–7.44 for the [Cr III cdta(H 2 O)] − complex and the pH range 5.56–8.56 for the [Cr III dtpa(H 2 O)] 2− complex. The reaction exhibited an uncommon second‐order dependence on [Cr III L(H 2 O)] n (L = cdta or dtpa and n =−1 or −2, respectively) and a first‐order dependence on [IO − 4 ]. At fixed reaction conditions, the reaction rate is described by Eq. (i). The third‐order rate constant, k 3 , varied with [H + ] according to Eq. (ii). equation image equation image A mechanism in which simultaneous one‐electron transfer from two [Cr III L(OH)] n −1 ions to I(VII) is proposed. The two [Cr III L(OH)] n −1 ions are bridged to I(VII) via the hydroxo group. Periodate ion is known to undergo rapid substitution or expansion of its coordination number from four to six. The activation parameters Δ H * and Δ S * were calculated using the Eyring equation. The relatively high negative values of Δ S * are consistent with an associative process preceding electron transfer. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 729–735, 2012" @default.
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- W2103138026 date "2012-07-17" @default.
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- W2103138026 title "Concurrent two one-electron transfer in the oxidation of chromium(III) complexes with<i>trans</i>-1,2-diaminocyclohexane-<i>N,N,N′,N′</i>-tetraacetate and diethylenetriaminepentaacetate ligands by periodate ion" @default.
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- W2103138026 doi "https://doi.org/10.1002/kin.20723" @default.
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