The compounds Cu(Dtc)2, Ni(Dtc)2, and Zn(Dtc)2 catalyze the decomposition ofα-phenylethyl hydroperoxide into free radicals and molecular products at 30 and 75°C (Dtc is N,N-diethyldithiocarbamate).
The products resulting from reactions of these dithiocarbamates also catalyze the decomposition ofα-phenylethyl hydroperoxide.
Catalytic decomposition ofα-phenylethyl hydroperoxide modifies the catalyst itself, leading to preferential reaction through a molecular decomposition mechanism.
The fact that stable RNO. radicals promoteα-phenylethyl hydroperoxide decomposition in the presence of Cu(Dtc)2 and Zn(Dtc)2, and inhibit decomposition in the presence of Cu(Tpa)2, hinders any attempt to use RNO. as radical acceptors in these systems [Tpa is bis (α-thiopicolinanilide)].
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The authors would like to thank A. N. Zverev for help in carrying out some of the experiments.
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Vinogradova, V.G. Catalysis of hydroperoxide decomposition by sulfur-containing metal chelates. Russ Chem Bull 27, 662–666 (1978). https://doi.org/10.1007/BF00925279
- Free Radical
- Metal Chelate