Unique pathway: The radical-initiated addition polymerization of MesP=CPh2 propagates through the ortho-bound CH3 group of the Mes moiety after CH bond activation (see scheme, Mes=2,4,6-trimethylphenyl, tht=tetrahydrothiophene, TEMPO=2,2,6,6-tetramethyl-l-piperidinoxyl). This unique isomerization polymerization mechanism contrasts the previously suggested head-to-tail enchainment typically observed for olefins.
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Siu et al. (2013) studied this question.
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