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

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

doi:10.1021/cs501962m

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

Journal Article · Wed Feb 11 00:00:00 UTC 2015 · ACS Catalysis

DOI: https://doi.org/10.1021/cs501962m · OSTI ID:1225382

Bataineh, Hajem ^[1]; Pestovsky, Oleg ^[1]; Bakac, Andreja ^[1]

Iowa State Univ., Ames, IA (United States)

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, k_cat = (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 k_Fe = (9.3 ± 0.3) × 10⁴ M^–1 s^–1. The similarity between the rate constants k_Fe and k_cat 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.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1225382

Report Number(s):: IS-J--8511; PII: 1185

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 3 Vol. 5; ISSN 2155-5435

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (42)

Kinetics of O�? and O3�? in alkaline aqueous solutions of hydrogen peroxide Gonzalez, M�nica C.; M�rtire, Daniel O. International Journal of Chemical Kinetics, Vol. 29, Issue 8 https://doi.org/10.1002/(SICI)1097-4601(1997)29:8<589::AID-KIN4>3.0.CO;2-Q	journal	January 1997
Reactions of the ferryl ion with some compounds found in cloud water Jacobsen, Frank; Holcman, Jerzy; Sehested, Knud International Journal of Chemical Kinetics, Vol. 30, Issue 3 https://doi.org/10.1002/(SICI)1097-4601(1998)30:3<215::AID-KIN7>3.0.CO;2-V	journal	January 1998
Aqueous FeIVO: Spectroscopic Identification and Oxo-Group Exchange Pestovsky, Oleg; Stoian, Sebastian; Bominaar, Emile L. Angewandte Chemie International Edition, Vol. 44, Issue 42 https://doi.org/10.1002/anie.200502686	journal	October 2005
The initiation process in the polymerization of tetrahydrofuran with carbonium ion salts Kuntz, Irving Journal of Polymer Science Part B: Polymer Letters, Vol. 4, Issue 6 https://doi.org/10.1002/pol.1966.110040611	journal	June 1966
1H-NMR and electrochemical studies on ligated iron(III)perchlorates in acetonitrile-d 3 Kirchner, Karl; Jedlicka, Rudolf; Schmid, Roland Monatshefte f�r Chemie Chemical Monthly, Vol. 123, Issue 3 https://doi.org/10.1007/BF00810466	journal	March 1992
Photochemical determination of the solubility of oxygen in various media Franco, Chris; Olmsted III, John Talanta, Vol. 37, Issue 9 https://doi.org/10.1016/0039-9140(90)80251-A	journal	September 1990
Oxidation of organic sulphides to sulphoxides by nitric acid catalyzed by FeBr3 and (FeBr3)2(DMSO)3 Suárez, Angela R.; Rossi, Laura I.; Martín, Sandra E. Tetrahedron Letters, Vol. 36, Issue 8 https://doi.org/10.1016/0040-4039(95)00033-9	journal	February 1995
The electrochemical oxidation of tetrahydrofuran in sulphuric acid solution Avgousti, Christiana; Georgolios, Nickos; Kyriacou, George Electrochimica Acta, Vol. 44, Issue 19 https://doi.org/10.1016/S0013-4686(99)00051-1	journal	May 1999
Catalytic aerobic oxidation of alcohols by Fe(NO3)3–FeBr3 Martı́n, Sandra E.; Suárez, Darı́o F. Tetrahedron Letters, Vol. 43, Issue 25 https://doi.org/10.1016/S0040-4039(02)00829-8	journal	June 2002
Ozone decomposition of hazardous chemical substance in organic solvents Nakano, Yoichi; Okawa, Kiyokazu; Nishijima, Wataru Water Research, Vol. 37, Issue 11 https://doi.org/10.1016/S0043-1354(03)00077-0	journal	June 2003
Kinetics of O^- and O₃^- in alkaline aqueous solutions Gonzalez, Monica C.; Martire, Daniel O. Water Science and Technology, Vol. 35, Issue 4 https://doi.org/10.1016/S0273-1223(97)00008-5	journal	January 1997
Ozone as primary oxidant in iron(III) porphyrin catalyzed hydroxylation of hydrocarbons Gross, Zeev; Simkhovich, Liliya Journal of Molecular Catalysis A: Chemical, Vol. 117, Issue 1-3 https://doi.org/10.1016/S1381-1169(96)00258-0	journal	March 1997
Aerobic oxidation of tetrahydrofuran by a series of iron (III) containing POSS compounds Hay, Michael T.; Geib, Steven J.; Pettner, Derek A. Polyhedron, Vol. 28, Issue 11 https://doi.org/10.1016/j.poly.2009.04.014	journal	July 2009
Iron(III)-(II) couple in acetonitrile. Oxidation of thiocyanate by iron(III) Kratochvil, Byron.; Long, Robert. Analytical Chemistry, Vol. 42, Issue 1 https://doi.org/10.1021/ac60283a025	journal	January 1970
How super is superoxide? Sawyer, Donald T.; Valentine, Joan S. Accounts of Chemical Research, Vol. 14, Issue 12 https://doi.org/10.1021/ar00072a005	journal	December 1981
Mechanism of Aromatic Amino Acid Hydroxylation ^† Fitzpatrick, Paul F. Biochemistry, Vol. 42, Issue 48 https://doi.org/10.1021/bi035656u	journal	December 2003
Standard Gibbs Free Energies of Reactions of Ozone with Free Radicals in Aqueous Solution: Quantum-Chemical Calculations Naumov, Sergej; von Sonntag, Clemens Environmental Science & Technology, Vol. 45, Issue 21 https://doi.org/10.1021/es2018658	journal	November 2011
Gas-Phase Heterogeneous Photocatalytic Oxidation of Ethanol: Pathways and Kinetic Modeling Nimlos, Mark R.; Wolfrum, Edward J.; Brewer, Matthew L. Environmental Science & Technology, Vol. 30, Issue 10 https://doi.org/10.1021/es9602298	journal	January 1996
Oxidation of ferrous ions by ozone in acidic solutions Loegager, Tine; Holcman, Jerzy; Sehested, Knud Inorganic Chemistry, Vol. 31, Issue 17, p. 3523-3529 https://doi.org/10.1021/ic00043a009	journal	August 1992
Iron(II) Triflate Salts as Convenient Substitutes for Perchlorate Salts: Crystal Structures of [Fe(H ₂ O) ₆ ](CF ₃ SO ₃ ) ₂ and Fe(MeCN) ₄ (CF ₃ SO ₃ ) ₂ Hagen, Karl S. Inorganic Chemistry, Vol. 39, Issue 25 https://doi.org/10.1021/ic000444w	journal	December 2000
Aqueous Ferryl(IV) Ion: Kinetics of Oxygen Atom Transfer To Substrates and Oxo Exchange with Solvent Water Pestovsky, Oleg; Bakac, Andreja Inorganic Chemistry, Vol. 45, Issue 2 https://doi.org/10.1021/ic051868z	journal	January 2006
Combined Experimental and Theoretical Study on Aromatic Hydroxylation by Mononuclear Nonheme Iron(IV)−Oxo Complexes de Visser, Sam P.; Oh, Kyungeun; Han, Ah-Rim Inorganic Chemistry, Vol. 46, Issue 11 https://doi.org/10.1021/ic700462h	journal	May 2007
Pulse radiolytic studies of the reaction of perhydroxyl/superoxide O2- with iron(II)/iron(III) ions. The reactivity of HO2/O2- with ferric ions and its implication on the occurrence of the Haber-Weiss reaction Rush, James D.; Bielski, Benon H. J. The Journal of Physical Chemistry, Vol. 89, Issue 23 https://doi.org/10.1021/j100269a035	journal	November 1985
Ozone decomposition in aqueous acetate solutions Sehested, K.; Holcman, J.; Bjergbakke, E. The Journal of Physical Chemistry, Vol. 91, Issue 9 https://doi.org/10.1021/j100293a032	journal	April 1987
Iron(II)-induced activation of hydroperoxides for the dehydrogenation and monooxygenation of organic substrates in acetonitrile Sugimoto, Hiroshi; Sawyer, Donald T. Journal of the American Chemical Society, Vol. 107, Issue 20 https://doi.org/10.1021/ja00306a018	journal	October 1985
Reactions of superoxide with iron porphyrins in aprotic solvents. A high spin ferric porphyrin peroxo complex McCandlish, Elizabeth; Miksztal, Andrew R.; Nappa, Mario Journal of the American Chemical Society, Vol. 102, Issue 12 https://doi.org/10.1021/ja00532a053	journal	June 1980
Mechanism of alkane oxidation by ozone in the presence and absence of iron(III) chloride Hellman, Thomas M.; Hamilton, Gordon A. Journal of the American Chemical Society, Vol. 96, Issue 5 https://doi.org/10.1021/ja00812a042	journal	March 1974
Pulse radiolysis studies. XV. Reactivity of the oxide radical ion and of the ozonide ion in aqueous solution Gall, Bonnie L.; Dorfman, Leon M. Journal of the American Chemical Society, Vol. 91, Issue 9 https://doi.org/10.1021/ja01037a002	journal	April 1969
On the Electrophilicity of Hydroxyl Radical: A Laser Flash Photolysis and Computational Study DeMatteo, Matthew P.; Poole, James S.; Shi, Xiaofeng Journal of the American Chemical Society, Vol. 127, Issue 19 https://doi.org/10.1021/ja043692q	journal	May 2005
Reactivity of Aqueous Fe(IV) in Hydride and Hydrogen Atom Transfer Reactions Pestovsky, Oleg; Bakac, Andreja Journal of the American Chemical Society, Vol. 126, Issue 42 https://doi.org/10.1021/ja0457112	journal	October 2004
How Solvent Modulates Hydroxyl Radical Reactivity in Hydrogen Atom Abstractions Mitroka, Susan; Zimmeck, Stephanie; Troya, Diego Journal of the American Chemical Society, Vol. 132, Issue 9 https://doi.org/10.1021/ja903856t	journal	February 2010
Determination of • OH, O 2 •- , and Hydroperoxide Yields in Ozone Reactions in Aqueous Solution † Flyunt, Roman; Leitzke, Achim; Mark, Gertraud The Journal of Physical Chemistry B, Vol. 107, Issue 30 https://doi.org/10.1021/jp022455b	journal	July 2003
Reaction of Peroxyl Radicals with Ozone in Water Lind, Johan; Merényi, Gábor; Johansson, Erik The Journal of Physical Chemistry A, Vol. 107, Issue 5 https://doi.org/10.1021/jp026323u	journal	February 2003
Study of the Electrochemical Reduction of Dioxygen in Acetonitrile in the Presence of Weak Acids Singh, Pradyumna S.; Evans, Dennis H. The Journal of Physical Chemistry B, Vol. 110, Issue 1 https://doi.org/10.1021/jp055296f	journal	January 2006
pH-induced mechanistic changeover from hydroxyl radicals to iron(iv) in the Fenton reaction Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja Chemical Science, Vol. 3, Issue 5 https://doi.org/10.1039/c2sc20099f	journal	January 2012
Kinetics and mechanism of the reactions of superoxide ion with hydrogen peroxide and hydroperoxides in an aprotic medium Afanas'ev, Igor B.; Kuprianova, Natalia S. Journal of the Chemical Society, Perkin Transactions 2, Issue 9 https://doi.org/10.1039/p29850001361	journal	January 1985
Reactivity of HO ₂ /O ⁻ ₂ Radicals in Aqueous Solution Bielski, Benon H. J.; Cabelli, Diane E.; Arudi, Ravindra L. Journal of Physical and Chemical Reference Data, Vol. 14, Issue 4 https://doi.org/10.1063/1.555739	journal	October 1985
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555805	journal	April 1988
Fenton chemistry at aqueous interfaces Enami, S.; Sakamoto, Y.; Colussi, A. J. Proceedings of the National Academy of Sciences, Vol. 111, Issue 2 https://doi.org/10.1073/pnas.1314885111	journal	December 2013
Reactions of alkoxy and alkyl peroxy radicals Batt, L. International Reviews in Physical Chemistry, Vol. 6, Issue 1 https://doi.org/10.1080/01442358709353401	journal	January 1987
Ozonolysis of Unsaturated Acids in Aqueous Solution: Acrylic, Methacrylic, Maleic, Fumaric and Muconic Acids Leitzke, Achim; Sonntag, Clemens von Ozone: Science & Engineering, Vol. 31, Issue 4 https://doi.org/10.1080/01919510903041354	journal	July 2009
Oxidation of benzyl alcohol and benzaldehyde with ozone in acetic acid Potapenko, E. V.; Andreev, P. Yu. Russian Journal of Applied Chemistry, Vol. 83, Issue 7 https://doi.org/10.1134/S1070427210070141	journal	July 2010

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

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