Ironii Catalysis In Oxidation Of Hydrocarbons With Ozone In Acetonitrile
Download Ironii Catalysis In Oxidation Of Hydrocarbons With Ozone In Acetonitrile full books in PDF, epub, and Kindle. Read online free Ironii Catalysis In Oxidation Of Hydrocarbons With Ozone In Acetonitrile ebook anywhere anytime directly on your device. Fast Download speed and no annoying ads. We cannot guarantee that every ebooks is available!
Iron(II) Catalysis in Oxidation of Hydrocarbons with Ozone in Acetonitrile
Author | : |
Publisher | : |
Total Pages | : 9 |
Release | : 2015 |
Genre | : |
ISBN | : |
Download Iron(II) Catalysis in Oxidation of Hydrocarbons with Ozone in Acetonitrile Book in PDF, Epub and Kindle
Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH3CN)62+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH3CN)62+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH3CN)62+] and [O3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, kcat = (8 ± 1) × 104 M-1 s-1, and that for (C2H5)2O is (5 ± 0.5) × 104 M-1 s-1. In the absence of substrate, Fe(CH3CN)62+ reacts with O3 with kFe = (9.3 ± 0.3) × 104 M-1 s-1. The similarity between the rate constants kFe and kcat strongly argues for Fe(CH3CN)62+/O3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH3CN)62+/O3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.
Iron(II) Catalysis in Oxidation of Hydrocarbons with Ozone in Acetonitrile Related Books
Pages: 9
Pages: 64
Pages: 506
Pages: 328
Pages: