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Title: Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

Abstract

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH 3CN) 6 2+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH 3CN) 6 2+-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(CH 3CN) 6 2+] and [O 3] 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, k cat = (8 ± 1) × 10 4 M –1 s –1, and that for (C 2H 5) 2O is (5 ± 0.5) × 10 4 M –1 s –1. In the absence of substrate, Fe(CH 3CN) 6 2+ reacts with O 3 with k Fe = (9.3 ± 0.3) × 10 4 M –1 s –1. The similarity between the rate constants k Fe and k cat strongly argues for Fe(CHmore » 3CN) 6 2+/O 3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH 3CN) 6 2+/O 3 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.« less

Authors:
 [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1225382
Report Number(s):
IS-J-8511
Journal ID: ISSN 2155-5435; PII: 1185
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; iron; ozone; oxidation; catalysis; alcohol; kinetics; mechanism

Citation Formats

Bataineh, Hajem, Pestovsky, Oleg, and Bakac, Andreja. Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile. United States: N. p., 2015. Web. doi:10.1021/cs501962m.
Bataineh, Hajem, Pestovsky, Oleg, & Bakac, Andreja. Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile. United States. doi:10.1021/cs501962m.
Bataineh, Hajem, Pestovsky, Oleg, and Bakac, Andreja. Wed . "Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile". United States. doi:10.1021/cs501962m. https://www.osti.gov/servlets/purl/1225382.
@article{osti_1225382,
title = {Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile},
author = {Bataineh, Hajem and Pestovsky, Oleg and Bakac, Andreja},
abstractNote = {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.},
doi = {10.1021/cs501962m},
journal = {ACS Catalysis},
number = 3,
volume = 5,
place = {United States},
year = {2015},
month = {2}
}

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