Oxidation of hydrocarbons and alcohols with peroxides catalyzed by new π-cymene osmium complexes

Vinogradov, Mikhail M.; Shul’pina, Lidia S.; Kozlov, Yuriy N.; Kudinov, Alexander R.; Ikonnikov, Nikolay S.; Shul’pin, Georgiy B.

doi:10.1016/j.jorganchem.2014.07.026

Cited by 25 publications

(10 citation statements)

References 103 publications

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“…One of these ways is the search of complexes of as yet unexplored metals. It has been found recently that osmium complexes catalyze the alkane oxidation with huge TONs [144][145][146]148]. For example, the oxidation of cyclohexane with hydrogen peroxide at 60˝C and low concentration of Os-catalyst (10´7 M) gave a turnover number (TON) of 200,000 after 24 h. [146].…”

Section: Discussionmentioning

confidence: 99%

“…During the past several decades, many metals have been studied in catalytic activation and functionalization of carbon-hydrogen bonds. The reader is directed to selected recent examples with gold [123], cobalt [124][125][126] chromium [127], copper [128][129][130][131] iron [132][133][134][135], iridium [136], manganese [137][138][139], molybdenum [140], nickel [141], osmium [142][143][144][145][146][147][148], palladium [149][150][151], rhenium [152], rhodium [153,154], ruthenium [155,156], and vanadium [157,158].…”

Section: Metal Ions Most Active In Oxidation Catalysismentioning

confidence: 99%

See 1 more Smart Citation

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

174

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This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst). Works of recent years (mainly 2010-2016) devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon-hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

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Section: Discussionmentioning

confidence: 99%

Section: Metal Ions Most Active In Oxidation Catalysismentioning

confidence: 99%

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

174

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“…This implied that the improvement of the mechanical properties of the In‐EPDM/NR composites might be due to the synergistic effect derived from the saturated rubber structure and in situ silica in the EPDM matrix. However, the thermal stability of HNR/NR including In‐HNR/NR and Si‐HNR/NR was not significantly improved possibly due to the effect of residual osmium catalyst in the HNR that could promote the oxidation of rubber hydrocarbon chain …”

Section: Resultsmentioning

confidence: 99%

Comparative behavior of in situ silica generation in saturated rubbers: EPDM and hydrogenated natural rubber

Ongwongsakul

Rempel

Poompradub

et al. 2017

J of Applied Polymer Sci

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Role of carbon‐carbon double (CC) bonds content and their position in ethylene‐propylene diene ter‐polymer (EPDM), hydrogenated natural rubber (HNR) and natural rubber (NR) on in situ silica formation using tetraethoxysilane (TEOS) as a silica precursor is comparatively investigated. Glass transition temperature (Tg) reflecting rubber chain flexibility is found as an important factor for in situ silica generation via swelling method. Despite of similar solubility parameters, NR has higher TEOS‐swelling degree resulting in the higher in situ silica content (30.8 phr) than EPDM (3.50 phr) and HNR (10.4–17.6 phr) due to the higher Tg of EPDM and HNR providing the less chain flexibility to be swollen in TEOS solution. The morphological analysis implies that CC bonds in saturated rubbers may be agglomeration sites for in situ silica particles. For practical applications, saturated rubbers containing in situ silica/NR vulcanizates showed the improvement of mechanical properties and resistance of thermal and ozone degradation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44748.

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“…The bond-selectivity parameter (1° : 2° : 3°; the relative normalized reactivities of hydrogen atoms at the primary, secondary and tertiary carbons) in the oxidation of methylcyclohexane (1.0 : 6.7 : 17.5) is close to the corresponding values found for the systems oxidizing alkanes with hydroxyl radicals (see, for example, Refs. [69][70][71][72][73][74][75]). The oxidation of cis-1,2-dimethylcyclohexane proceeds non-stereoselectively because the trans/cis ratio [the ratio of isomers of tert-alcohols with mutual trans-and cis-orientation of two methyl groups] of isomeric alcohols (after reduction with PPh3) was 0.8.…”

Section: Selectivity In the Alkane Oxidationsmentioning

confidence: 99%

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

Yalymov

Bilyachenko

Levitsky

et al. 2017

Preprint

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Two types of heterometallic (Fe(III),Na) silsesquioxanes [Ph5Si5O10]2[Ph10Si10O21]Fe6(O2‒)2Na7(H3O+)(MeOH)2(MeCN)4.5.1.25(MeCN), I, and [Ph5Si5O10]2[Ph4Si4O8]2Fe6Na6(O2‒)3(MeCN)8.5(H2O)8.44, II, were obtained and characterized. X-Ray studies established distinctive structures of both products, with pair of Fe(III)-O-based triangles surrounded by siloxanolate ligands, giving fascinating cage architectures. Complex II proved to be catalytically active in the formation of amides from alcohols and amines, thus becoming a rare example of metallasilsesquioxanes performing homogeneous catalysis. Benzene, cyclohexane and other alkanes, as well as alcohols, can be oxidized in acetonitrile solution to phenol, the corresponding alkyl hydroperoxides and ketones, respectively, by hydrogen peroxide in air in the presence of catalytic amounts of complex II and trifluoroacetic acid. Thus, the cyclohexane oxidation at 20 °C gave oxygenates in very high for alkanes yield (48% based on alkane). The kinetic behaviour of the system indicates that the mechanism includes the formation of hydroxyl radicals generated from hydrogen peroxide in its interaction with diiron species. The latter are formed via monomerization of starting hexairon complex with further dimerization of the monomers.

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Oxidation of hydrocarbons and alcohols with peroxides catalyzed by new π-cymene osmium complexes

Cited by 25 publications

References 103 publications

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Comparative behavior of in situ silica generation in saturated rubbers: EPDM and hydrogenated natural rubber

High Catalytic Activity of Heterometallic (Fe<sub>6</sub>Na<sub>7 </sub>and Fe<sub>6</sub>Na<sub>6</sub>) Cage Silsesquioxanes in Oxidations with Peroxides

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