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- W2000817882 abstract "The stoichiometry of the OsO4-catalysed oxidation of phosphinite (R = H) and phenylphosphinite ion (R = C6H5) by alkaline hexacyanoferrate(III) is expressed by the equation:2Fe(CN)63-+RHPO2-+2OH-→OsO42Fe(CN)64-+RHPO3-+H2O The proposed mechanism is based on the kinetics which has a zero order dependence in Fe(CN)63-, first order in OsO4 and one component of the rate is independent of [OH−]. The Michaelis-Menten kinetics with respect to RHPO2- is supportive of the complex OsO4(OH)RHPO22-, formed from RHPO2- and OsO4(OH)− ions, which decomposes with the rate constant k in the rate determining step (Mean: ΔHk‡=19±6, ΔGk‡=73±2 and -ΔSk‡=182±18 for H2PO2-, and ΔHk‡=18±3, ΔGk‡=74±3kJmol-1 and -ΔSk‡=188±11JK-1mol-1 for C6H5HPO2-). The formation constant β for the complex is independent of OH− (ΔH∘=29±1, ΔG∘=-8±1 and ΔS∘=122±5 for H2PO2-, and ΔH∘=8±1, ΔG∘=-10±1kJmol-1 and ΔS∘=62±3JK-1mol-1 for C6H5HPO2-). However, the formation of the complex [OsO4(OH)2RHPO2]3− is considered unlikely in view of the relatively strong repulsive forces between OsO4(OH)22- and RHPO2- ions which react by bimolecular collision with rate constant k2 (Mean: ΔHk2K2‡=33±8, ΔGk2K2‡=70±9 and -ΔSk2K2‡=121±23 for H2PO2-, and ΔHk2K2‡=30±4, ΔGk2K2‡=71±6kJmol-1 and -ΔSk2K2‡‡=140±14JK-1mol-1forC6H5HPO2-). The ‘inactive’ tautomeric form RHPO2- is the considered reactive entity." @default.
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- W2000817882 date "2008-11-01" @default.
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- W2000817882 title "Kinetics and mechanism of the Os(VIII)-catalysed oxidation of hypophosphite and phenylphosphinite ion by alkaline hexacyanoferrate(III) ion" @default.
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- W2000817882 doi "https://doi.org/10.1016/j.poly.2008.08.002" @default.
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