Catalyzed radical termination in the presence of tellanyl radicals
Résumé
The decomposition of the diazo initiator dimethyl 2,2′‐azobis(isobutyrate) (V‐601), generating the Me2C.(CO2Me) radical, affords essentially the same fraction of disproportionation and combination in media with a large range of viscosity (C6D6, [D6]DMSO, and PEG 200) in the 25–100 °C range. This is in stark contrast to recent results by Yamago et al. on the same radical generated from Me2C(TeMe)(CO2Me) and on other X‐TeR systems (X=polymer chain or unimer model; R=Me, Ph). The discrepancy is rationalized on the basis of an unprecedented RTe.‐catalyzed radical disproportionation, with support from DFT calculations and photochemicaL V‐601 decomposition in the presence of Te2Ph2.
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