Kinetics and Mechanism of the Chromium(VI) Oxidation of Some Primary Alcohols in the Presence of Heteroaromatic N-bases in Aqueous Acetonitrile Media
作者： Subbiah Meenakshisundaram , N. Sarathi
DOI: 10.1007/S11243-006-0018-0
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摘要: Heteroaromatic N-bases picolinic acid (PA) and 1,10-phenanthroline (Phen) in MeCN smoothly catalyse the chromium(VI) oxidation of some primary alcohols to corresponding carbonyl compounds. The depletion shows complicated kinetic behaviour involving a fast reaction ca. 25% consumption followed by slow one. Cr(VI)-PA Cr(VI)–Phen complexes are believed be probable reactive electrophiles. u.v–vis spectrum establishes formation ternary complex data can rationalized envisaging its redox decomposition. low dielectric constant medium assists enhances reactivity. Curvature first order plots roughly indicates that chromium(V) react at comparable rate complicate parameters. CH3OH reacts six times faster than CD3OD this study strongly favours hydride transfer mechanism. reactivities aliphatic much greater benzyl alcohol implies predominance inductive effect over resonance effect.
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