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• W2582701049 abstract "A study of the kinetics and mechanism of the oxidation of a series of electron-rich and electron-deficient benzyl alcohols and cyclohexanol with high-valent manganese oxo species formed by the reaction of meso-tetrakis(2,6-dichlorophenyl)porphyrinatomanganese(III) acetate [Mn(TDClPP)(OAc)] and tetra-n-butylammonium oxone (TBAO) in the presence of imidazole (ImH) are reported. The use of Mn(TDClPP)(OAc), ImH, and TBAO in a 1:15:1000 molar ratio led to the exclusive formation of [(ImH)MnV(O)(TDClPP)]+ (λmax = 408 nm), whereas a mixture of [(ImH)MnV(O)(TDClPP)]+, (ImH)MnIV(O)(TDClPP) (λmax = 421 nm), and (ImH)(peroxymonopersulfate)MnIII(TDClPP) (λmax = 473 nm) was observed for molar ratios lower than this. The formation of [(ImH)MnV(O)(TDClPP)]+ and (ImH)MnIV(O)(TDClPP) from the catalyst precursor was evidenced in the UV/Vis absorption spectrum of the intermediates at 273 K in dichloromethane. Owing to the different reactivities of the high-valent intermediates towards the oxidation of alcohols, a biphasic mechanism was observed. The observed (kobs) and second-order (k2) rate constants of oxygen-atom transfer from high-valent MnV(O) species to the substrates were evaluated by monitoring the absorption changes at λ = 473 nm. The Hammett treatment of the oxidation data gave a slope (ϱ) of –0.87, which is consistent with a radical mechanism. Furthermore, a strong correlation between the rate constants and the C–H bond dissociation energies (BDEs) of the alcohols suggests the involvement of H-atom abstraction in the mechanism of the oxidation reaction. Interestingly, a negative temperature dependence of the reaction rate was observed for the oxidation of benzyl alcohol from 273 to 298 K. Furthermore, the high-valent MnV(O) and MnIV(O) species may be distinguished through their significantly different activities towards the oxidation of alcohols." @default.
• W2582701049 created "2017-02-03" @default.
• W2582701049 creator A5040452482 @default.
• W2582701049 creator A5087697150 @default.
• W2582701049 date "2017-04-03" @default.
• W2582701049 modified "2023-09-27" @default.
• W2582701049 title "Evidence on the Nature of the Active Oxidants Involved in the Oxidation of Alcohols with Oxone Catalyzed by an Electron-Deficient Manganese Porphyrin: A Combined Kinetic and Mechanistic Study" @default.
• W2582701049 cites W1471589903 @default.
• W2582701049 cites W1874663204 @default.
• W2582701049 cites W1920231800 @default.
• W2582701049 cites W1943768787 @default.
• W2582701049 cites W1968048104 @default.
• W2582701049 cites W1969240557 @default.
• W2582701049 cites W1972127956 @default.
• W2582701049 cites W1974475845 @default.
• W2582701049 cites W1974655516 @default.
• W2582701049 cites W1978340802 @default.
• W2582701049 cites W1978802654 @default.
• W2582701049 cites W1979140627 @default.
• W2582701049 cites W1983346165 @default.
• W2582701049 cites W1983514748 @default.
• W2582701049 cites W1984728369 @default.
• W2582701049 cites W1987133302 @default.
• W2582701049 cites W1990514630 @default.
• W2582701049 cites W1993715587 @default.
• W2582701049 cites W1993809008 @default.
• W2582701049 cites W1997112178 @default.
• W2582701049 cites W1998918374 @default.
• W2582701049 cites W2001127597 @default.
• W2582701049 cites W2006366087 @default.
• W2582701049 cites W2008658995 @default.
• W2582701049 cites W2010324195 @default.
• W2582701049 cites W2013358573 @default.
• W2582701049 cites W2015165733 @default.
• W2582701049 cites W2018935119 @default.
• W2582701049 cites W2020457705 @default.
• W2582701049 cites W2025283388 @default.
• W2582701049 cites W2026919377 @default.
• W2582701049 cites W2027431505 @default.
• W2582701049 cites W2027638545 @default.
• W2582701049 cites W2027656257 @default.
• W2582701049 cites W2030633522 @default.
• W2582701049 cites W2033020343 @default.
• W2582701049 cites W2034265417 @default.
• W2582701049 cites W2034796508 @default.
• W2582701049 cites W2035265051 @default.
• W2582701049 cites W2038783840 @default.
• W2582701049 cites W2047920186 @default.
• W2582701049 cites W2049865119 @default.
• W2582701049 cites W2051168617 @default.
• W2582701049 cites W2053172978 @default.
• W2582701049 cites W2059692975 @default.
• W2582701049 cites W2062666384 @default.
• W2582701049 cites W2065000954 @default.
• W2582701049 cites W2065788902 @default.
• W2582701049 cites W2066069109 @default.
• W2582701049 cites W2067647330 @default.
• W2582701049 cites W2068417554 @default.
• W2582701049 cites W2070671643 @default.
• W2582701049 cites W2070836098 @default.
• W2582701049 cites W207162005 @default.
• W2582701049 cites W2073356400 @default.
• W2582701049 cites W2073485451 @default.
• W2582701049 cites W2075353516 @default.
• W2582701049 cites W2076560798 @default.
• W2582701049 cites W2077621515 @default.
• W2582701049 cites W2082334727 @default.
• W2582701049 cites W2083302542 @default.
• W2582701049 cites W2083630420 @default.
• W2582701049 cites W2084052917 @default.
• W2582701049 cites W2085831526 @default.
• W2582701049 cites W2089437604 @default.
• W2582701049 cites W2090129581 @default.
• W2582701049 cites W2094289644 @default.
• W2582701049 cites W2104285058 @default.
• W2582701049 cites W2105248135 @default.
• W2582701049 cites W2108116671 @default.
• W2582701049 cites W2115398499 @default.
• W2582701049 cites W2128780021 @default.
• W2582701049 cites W2130069956 @default.
• W2582701049 cites W2133416961 @default.
• W2582701049 cites W2140158011 @default.
• W2582701049 cites W2147398137 @default.
• W2582701049 cites W2147899939 @default.
• W2582701049 cites W2152087962 @default.
• W2582701049 cites W2152919588 @default.
• W2582701049 cites W2154707380 @default.
• W2582701049 cites W2155860547 @default.
• W2582701049 cites W2160377397 @default.
• W2582701049 cites W2162065081 @default.
• W2582701049 cites W2162441605 @default.
• W2582701049 cites W2163851941 @default.
• W2582701049 cites W2167204985 @default.
• W2582701049 cites W2171396825 @default.
• W2582701049 cites W2261292770 @default.
• W2582701049 cites W2293593750 @default.
• W2582701049 cites W2323725487 @default.
• W2582701049 cites W2330965523 @default.
• W2582701049 cites W2331358663 @default.
• W2582701049 cites W2335669903 @default.

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