Oxidation of alkanes and benzene with hydrogen peroxide catalyzed by ferrocene in the presence of acids

Author(s)

Shul'pina, Lidia S. ^[1] ; Kudinov, Aleksandr R. ^[1] ; Mandelli, Dalmo ^[2] ; Carvalho, Wagner A. ^[2] ; Kozlov, Yuriy N. ^[3] ; Vinogradov, Mikhail M. ^[1] ; Ikonnikov, Nikolay S. ^[1] ; Shul'pin, Georgiy B. ^[3]

Affiliation

^[1] Russian Acad Sci, Nesmeyanov Inst Organoelement Cpds, Moscow 119991 - Russia

^[2] Fed Univ ABC UFABC, Ctr Nat & Human Sci, BR-09210170 Santo Andre, SP - Brazil

^[3] Russian Acad Sci, Semenov Inst Chem Phys, Moscow 119991 - Russia

• Document type: Journal article
• Source: JOURNAL OF ORGANOMETALLIC CHEMISTRY; v. 793, p. 217-231, SEP 15 2015.
• Web of Science Citations: 17

Abstract

The efficient (turnover numbers attained 1200) oxidation of alkanes to the corresponding alkyl hydroperoxides by H2O2 in the presence of catalytic amounts of ferrocene proceeds in MeCN at 40-50 degrees C. Benzene is oxidized in the same system to phenol. An obligatory component of the catalytic system for both reactions is pyrazine-2-carboxylic acid (PCA) or trifluoroacetic acid (TFA). Kinetic study as well as selectivity parameters testified that the oxidation proceeds with the participation of hydroxyl radicals. In the case of PCA as a co-catalyst the initial rate W-0 of the reaction with both cyclohexane and benzene depends quadratically on {[}Cp2Fe](0) whereas the two reactions in the presence of TFA are of half order in ferrocene. The ferrocene-catalyzed reaction of cyclohexane with H-2 O-16(2) in an atmosphere of labeled O-18(2) gave after 2 h a mixture of labeled and unlabeled cyclohexyl hydroperoxide (total yield 20% based on starting cyclohexane) containing up to 69% of O-18 (the analysis was after reduction of cyclohexyl hydroperoxide into cyclohexanol with PPh3). (C) 2015 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 14/09136-5 - Photochemical and thermal oxidations of hydrocarbons catalyzed by complexes of transition metals (V, Cu, Os, Fe, Mn and others)
• Grantee: Dalmo Mandelli
• Support Opportunities: Research Grants - Visiting Researcher Grant - International