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

Journal Article · · ACS Catalysis
DOI:https://doi.org/10.1021/cs501962m· OSTI ID:1225382
 [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
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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.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1225382
Report Number(s):
IS-J-8511; PII: 1185
Journal Information:
ACS Catalysis, Vol. 5, Issue 3; ISSN 2155-5435
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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Cited By (2)

Design of recyclable TEMPO derivatives bearing an ionic liquid moiety and N,N-bidentate group for highly efficient Cu( i )-catalyzed conversion of alcohols into aldehydes and imines journal January 2016
Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation journal December 2016

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
iron
ozone
oxidation
catalysis
alcohol
kinetics
mechanism