Kinetics and mechanism of ruthenium tetroxide catalysed oxidation of cyclic alcohols by bromate in a base (original) (raw)
1991, Transition Metal Chemistry
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The study investigates the kinetics and mechanism of the oxidation of cyclic alcohols by bromate in the presence of ruthenium tetroxide as a catalyst. Through a series of experiments, reaction rates were measured, and the influence of different concentrations of reactants, temperature, and pH on the oxidation process was analyzed. The data suggested a complex reaction mechanism involving multiple steps, highlighting the role of ruthenium tetroxide in enhancing the oxidation rate. This work contributes to the understanding of oxidizing reactions in organic chemistry and offers insights for potential applications in synthetic processes.
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Journal of the American Chemical Society, 2001
The combination of RuCl 2 (PPh 3 ) 3 and TEMPO affords an efficient catalytic system for the aerobic oxidation of a variety of primary and secondary alcohols, giving the corresponding aldehydes and ketones, in >99% selectivity in all cases. The Ru/TEMPO system displayed a preference for primary vs secondary alcohols. Results from Hammett correlation studies (F ) -0.58) and the primary kinetic isotope effect (k H /k D ) 5.1) for the catalytic aerobic benzyl alcohol oxidations are inconsistent with either an oxoruthenium (OdRu) or an oxoammonium based mechanism. We postulate a hydridometal mechanism, involving a "RuH 2 (PPh 3 ) 3 " species as the active catalyst. TEMPO acts as a hydrogen transfer mediator and is either regenerated by oxygen, under catalytic aerobic conditions, or converted to TEMPH under stoichiometric anaerobic conditions.
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