BF3-activated oxidation of alkanes by MnO4 -

Journal of the American Chemical Society
William W Y LamZhenyang Lin

Abstract

The oxidation of alkanes and arylalkanes by KMnO(4) in CH(3)CN is greatly accelerated by the presence of just a few equivalents of BF(3), the reaction occurring readily at room temperature. Carbonyl compounds are the predominant products in the oxidation of secondary C-H bonds. Spectrophotometric and kinetics studies show that BF(3) forms an adduct with KMnO(4) in CH(3)CN, [BF(3).MnO(4)](-), which is the active species responsible for the oxidation of C-H bonds. The rate constant for the oxidation of toluene by [BF(3).MnO(4)](-) is over 7 orders of magnitude faster than by MnO(4)(-) alone. The kinetic isotope effects for the oxidation of cyclohexane, toluene, and ethylbenzene at 25.0 degrees C are as follows: k(C6H12)/k(C6D12) = 5.3 +/- 0.6, k(C7H8)/k(C7D8) = 6.8 +/- 0.5, k(C8H10)/k(C8D10) = 7.1 +/- 0.5. The rate-limiting step for all of these reactions is most likely hydrogen-atom transfer from the substrate to an oxo group of the adduct. A good linear correlation between log(rate constant) and C-H bond energies of the hydrocarbons is found. The accelerating effect of BF(3) on the oxidation of methane by MnO(4)(-) has been studied computationally by the Density Functional Theory (DFT) method. A significant decrease in the reac...Continue Reading

References

May 7, 1997·Inorganic Chemistry·Kimberly A. GardnerJames M. Mayer
Feb 20, 2002·Chemical Reviews·Alexander E. Shilov, Georgiy B. Shul'pin

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Citations

Jun 7, 2012·Journal of the American Chemical Society·Pannee LeeladeeDavid P Goldberg
Jan 18, 2013·Journal of the American Chemical Society·Junying ChenWonwoo Nam
Jun 8, 2013·Journal of the American Chemical Society·Heejung YoonShunichi Fuhkuzumi
Mar 19, 2009·Journal of the American Chemical Society·Christopher R WaidmannJames M Mayer
Mar 2, 2011·Chemical Communications : Chem Comm·Shek-Man YiuTai-Chu Lau
May 27, 2011·Chemical Communications : Chem Comm·Hongxia DuTai-Chu Lau
Mar 11, 2017·Chemical Reviews·Xiao-Song XueJin-Pei Cheng
Mar 16, 2017·Journal of the American Chemical Society·Shivaiah VaddypallyMichael J Zdilla
Sep 22, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Shuhao QinGuochuan Yin
May 6, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Jisheng ZhangGuochuan Yin
Apr 24, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Cholho ChoeGuochuan Yin
Jan 15, 2014·Chemical Science·Caroline T Saouma, James M Mayer
Jun 5, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Andrew J LewisEric J Schelter
Jan 14, 2010·Chemical Reviews·David BalcellsOdile Eisenstein
Oct 12, 2010·Chemical Reviews·Jeffrey J WarrenJames M Mayer
May 31, 2014·Inorganic Chemistry·Regina A BagliaDavid P Goldberg
Aug 14, 2020·Journal of the American Chemical Society·Shan-Shan XueWonwoo Nam
May 13, 2015·Journal of the American Chemical Society·Jan Paulo T ZaragozaDavid P Goldberg
Oct 9, 2018·Journal of the American Chemical Society·Brandon E HainesDjamaladdin G Musaev
Feb 2, 2019·Journal of the American Chemical Society·Yingying Liu, Tai-Chu Lau

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