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Kinetics and Mechanism of the Chromium(VI) Oxidation of Some Primary Alcohols in the Presence of Heteroaromatic N-bases in Aqueous Acetonitrile Media

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Abstract

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

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Authors and Affiliations

  1. Department of Chemistry, Annamalai University, Annamalainagar, 608 002, India

    Subbiah Meenakshisundaram & N. Sarathi

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  1. Subbiah Meenakshisundaram
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  2. N. Sarathi
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Correspondence to Subbiah Meenakshisundaram.

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Meenakshisundaram, S., Sarathi, N. Kinetics and Mechanism of the Chromium(VI) Oxidation of Some Primary Alcohols in the Presence of Heteroaromatic N-bases in Aqueous Acetonitrile Media. Transition Met Chem 31, 569–574 (2006). https://doi.org/10.1007/s11243-006-0018-0

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