Decamethylosmocene-catalyzed efficient oxidation of saturated and aromatic hydrocarbons and alcohols with hydrogen peroxide in the presence of pyridine |
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| Authors: | Georgiy B Shul’pin Marina V Kirillova Yuriy N Kozlov Lidia S Shul’pina Alexander R Kudinov Armando JL Pombeiro |
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| Affiliation: | 1. Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow 119991, Russia;2. Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049–001 Lisbon, Portugal;3. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, Moscow 119991, Russia;1. A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991 Moscow, Russian Federation;2. Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation;3. N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation;1. Department of Chemistry, Faculty of Education, Ain Shams University, Roxy, 11711 Cairo, Egypt;2. Thin Film Laboratory, Department of Physics, Faculty of Education, Ain Shams University, Roxy, 11711 Cairo, Egypt;3. Department of Physics, Faculty of Science and Arts, Al Jouf University, Saudi Arabia;4. Electronic Materials Department, Advanced Technology and New Material Institute, City for Scientific Research and Technological Applications, New Borg El Arab City, 21934 Alexandria, Egypt;1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation;2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991 Moscow, Russian Federation;1. Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation;2. N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation;3. National Research Centre ‘Kurchatov Institute’, 123098 Moscow, Russian Federation |
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| Abstract: | Decamethylosmocene, (Me5C5)2Os (1), is a pre-catalyst in a very efficient oxidation of alkanes with hydrogen peroxide in acetonitrile at 20–60 °C. The reaction proceeds with a substantial lag period that can be reduced by the addition of pyridine in a small concentration. The lag period can be removed if 1 is incubated with pyridine and/or H2O2 in MeCN prior to the alkane oxidation. Alkanes, RH, are oxidized primarily to the corresponding alkyl hydroperoxides, ROOH. Turnover numbers attain 51,000 in the case of cyclohexane (maximum turnover frequency was 6000 h?1) and 3600 in the case of ethane. The oxidation of benzene and styrene also occurs with a lag period to afford phenol and benzaldehyde, respectively. A kinetic study of cyclohexane oxidation and selectivity parameters (measured in the oxidation of n-heptane, methylcyclohexane, isooctane, cis- and trans-dimethylcyclohexanes) indicates that the oxidation of saturated, olefinic, and aromatic hydrocarbons proceeds with the participation of hydroxyl radicals. The 1/H2O2/py/MeCN system also oxidizes 1-phenylethanol to acetophenone. |
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