Complex formation during the liquid phase catalytic oxidation of hydrocarbons

Digurov, N. G.; Zakharova, V. I.; Kamneva, A.I.

doi:10.1016/0031-6458(66)90043-8

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“…This is supported by literature and our findings that indicate the presence of high electron density on the terminal oxygen of the peroxo moiety which would lend itself to rapid dimerization [57,58]. In this case, no precipitation occurred but the onset of deactivation was followed by a gradual change in color of the solution from orange to bright yellow which indicates a change to the local electronic structure or coordination of the metal [59]. It is possible that this color is also caused by ligand decomposition as typically the color of H 2 -salen is bright yellow.…”

Section: Spectroscopic Characterizationsupporting

confidence: 90%

An electrochemical study of cobalt-salen (N,N′-bis(salicylidene)ethylenediaminocobalt(II) in the oxidation of syringyl alcohol in acetonitrile

2020

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The reactivity of cobalt(II) complexes with molecular oxygen is a heavily studied and extremely important catalytic system. These interactions result in the formation of metal-dioxygen adducts that are responsible for numerous cobalt-catalyzed oxidations. In the case of 4-coordinate cobalt salen [Co(salen)] complexes, the formation of catalytically active, mononuclear, superoxo adducts in the presence of a secondary, N-donor ligand has been demonstrated [Co(salen)pyr-O 2 ]. In batch reactions, these adducts are known to readily oxidize certain para-substituted phenolic compounds resulting in benzoquinones in high yield. Para-phenolic model compounds have been used to demonstrate the potential use of cobalt Schiff base complexes in the oxidation of lignin biomass. This work investigates the redox behavior of the Co(salen)pyr-O 2 adduct as a potential recyclable electrocatalyst. Using traditional electrochemical techniques, the activity of the Co(salen)pyr-O 2 adduct is evaluated as it applies to the oxidation of the substrate syringyl alcohol (4-(hydroxymethyl)-2,6-dimethoxy-phenol) in acetonitrile. Typical EC′ electrochemical behavior is reported showing a near linear relationship between substrate concentration and peak current density (J p ) up to 200 mV s −1 . Electrochemical titration of catalytic amounts of Co(salen) with pyridine in the presence of excess oxygen and substrate indicate that the one-electron oxidation of Co(salen)pyr-O 2 H is reversible up to 2:1 pyridine to cobalt. However EPR characterization of electrolysis experiments with Co(salen)pyr-O 2 in the presence of excess substrate show evidence for the deactivation of the catalyst system after two hours, indicating possible poor ligand stability or the occurrence of an inhibiting side reaction under reaction conditions.

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Section: Spectroscopic Characterizationsupporting

confidence: 90%