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The Radical and Ion-Radical Mechanism of Polymerization of 2,6-Xylenol. II. The Reactivity of Aryloxy Radicals with Соррег(П) Complexes

A. Tkáč and J. Kresta

Institute of Chemical Physics, Department of Physical Chemistry, Slovak Technical University, Bratislava 1

 

Abstract: Free tri-čerč-butyl-phenoxy radical was used as model compound for studying the reactivity of aryloxy radicals with Cu(II)-cyclohexylamině complexes (as homogeneous catalyst of oxidative coupling of 2,6-dimethylphenol). The analysis of the EPR signals leads to the conclusion that electron transfer from the free radical to Cu(II) takes place if Cu(II) is not fully coordinated with eyelohexylamině. In complexes with the copper atom firmly bound in chelate groups (ethylacetylacetonate) no electron transfer occurs. Not only the tri-tert-butyl-, but also the polymer phenoxy radicals react very effectively with the catalytic Cu(II)-cyclohexylamine complexes. The polymer phenoxy radical in contrast with the tri-tert-butyl radical is not reactive with CuCI2 molecules.

Full paper in Portable Document Format: 251a3.pdf

 

Chemical Papers 25 (1) 3–8 (1971)

Tuesday, September 27, 2022

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