Oxidation of alcohols with hydrogen peroxide catalyzed by soluble iron and osmium derivatives 

Abstract

Osmium chloride OsCl 3 efficiently catalyzes (yields of products up to 90%, turnover numbers (TON) up to 1500) the oxidation of 2-cyanoethanol with hydrogen peroxide to produce the corresponding aldehyde and acid. Oxidation of isopropanol over OsCl 3 gave acetone in 58% yield. The reactions were carried out either in acetonitrile or without any solvent. The analogous iron compound FeCl 3 was found to be less efficient in the oxidation of 2-cyanoethanol (yields of products up to 67%, TON up to 135). Oxidation of isopropanol in this case gave acetone (yield 53%) and acetic acid (yield 11%). Some other soluble derivatives of iron or osmium exhibited noticeably lower catalytic activity in the alcohol oxidation with H 2 O 2 .

Oxidation of alkanes and alcohols with hydrogen peroxide catalyzed by complex Os3(CO)10(µ‐H)2

“…It is known that in the case of oxidations with the participation of hydroxyl radicals (for example, for the systems H 2 O 2 -hν, H 2 O 2 -vanadate-PCA in acetonitrile, see Shul'pin et al [2t,7a,d,e] ), even when substrates react with HO · with the rate constant lower that that for 1-phenylethanol, value W 0 practically does not depend on substrate concentration if this concentration is higher than ca 0.5 M. It follows from the data demonstrated in Fig. 4(A) that the rate of 1-phenylethanol oxidation on catalyst 1 continues to grow even at [6] 0 > 0.5 M, despite the rate constant of the interaction between 6 and HO · being approximately one order of magnitude higher than the corresponding constant for cyclohexane.…”

“…[4] In contrast, relatively few publications have been devoted to osmiumcatalyzed oxidations of saturated and aromatic hydrocarbons and alcohols. [5,6] Here, we have explored the possibility of complex Os 3 (CO) 10 (µ-H) 2 to catalyze oxidation of alkanes and alcohols with hydrogen peroxide.…”

Hydrogenated natural rubber blends: Aspect on thermal stability and oxidative behavior

“…Some previous research reported that carbonyl osmium complexes had the potential to be a catalyst for oxidation of alkanes and alcohols with hydrogen peroxide. 27,28 Therefore, the EPDM/NR vulcanizates cured using the PV system exhibited a comparatively higher retention of mechanical properties (72.3% for TS and 92.1% for EB).…”

Fe-Catalyzed Oxidation Reactions of Olefins, Alkanes, and Alcohols: Involvement of Oxo- and Peroxo Complexes

“…Often iron oxo species are proposed as catalytic intermediates. Examples include the simple combination of FeCl 3 and hydrogen peroxide, which is known to be of moderate activity in alcohol oxidations as shown in the case of 2-cyanoethanol [137]. An FeCl 3 -TEMPO-NaNO 2 catalyst system using air as oxidant was introduced in 2005 [138].…”