The role of onium salts in the oxidation of hydrocarbons by O2 catalysed by cationic phase-transfer reagents

Literature Information

Publication Date 2000-08-04
DOI 10.1039/B002558P
Impact Factor 3.676
Authors

László J. Csányi, Károly Jáky, István Pálinkó, Antal Rockenbauer, László Korecz


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Abstract

Experimental and theoretical evidence is presented that cationic phase-transfer catalysts promote the homolytic decomposition of hydroperoxide initiators into radicals, this being a fundamental step in the catalysis of the oxidation of hydrocarbons by O2. Such decomposition of the model substance tert-butyl hydroperoxide (t-BHP) results in O2, tert-butanol (90–95%) di-tert-butyl peroxide (5–10%) and traces of CO2. The stoichiometric ratio Δ[t-BHP]/ΔO2 was found to have a value of 2, independently of the nature of the counteranion present. It is assumed that the interaction between hydroperoxide and onium cation is mainly electrostatic in nature and that its effectivity depends on the positive charge density on the onium cation, which is controlled by the nature and dimensions of the counteranion. The role of water in the decomposition of t-BHP is also elucidated.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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