Abstract
The MnIV complex of tetra-deprotonated 1,8-bis(2-hydroxybenzamide)-3,6-diazaoctane (MnIVL) engrossed in phenolate-amido-amine coordination is reduced by HSO −3 and SO 2−3 in the pH range 3.15–7.3 displaying biphasic kinetics, the MnIIIL− being the reactive intermediate. The MnIIIL− species has been characterized by u.v.–vis. spectra {λ max, (ε, dm3 mol−1 cm−1): 285(15 570), 330 sh (7570), 469(6472), 520 sh (5665), pH=5.42}. SO 2−4 was the major oxidation product of SIV; dithionate is also formed (18 ± 2% of [MnIV] T ) which suggests that dimerisation of SO −•3 is competitive with its fast oxidation by MnIV/III. The rates and activation parameters for MnIVL + HSO −3 (SO 2−3 ) → MnIIIL−; MnIIIL− + HSO −3 (SO 2−3 ) → MnIIL2− are reported at 28.5–45.0 °C (I=0.3 mol dm−3, 10% (v/v) MeOH + H2O). Reduction by SO 2−3 is ca. eight times faster than by HSO −3 both for MnIVL and MnIIIL−. There was no evidence of HSO −3 /SO 2−3 coordination to the Mn centre indicating an outer sphere (ET) mechanism which is further supported by an isokinetic relationship. The self exchange rate constant (k22) for the redox couple, MnIIIL−/MnIVL (1.5 × 106 dm3 mol−1 s−1 at 25 °C) is reported.
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Nayak, S., Dash, A.C. Reactions of sulfur(IV) with an octahedral manganese(IV) complex of 1,8-bis(2-hydroxy benzamido)-3,6-diaza octane: the role of phenolate–amide–amine coordination. Transition Met Chem 30, 560–568 (2005). https://doi.org/10.1007/s11243-005-2385-3
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DOI: https://doi.org/10.1007/s11243-005-2385-3