Isomerization Polymerization of the Phosphaalkene MesP[DOUBLE BOND]CPh2: An Alternative Microstructure for Poly(methylenephosphine)s


  • We thank the Natural Sciences and Engineering Research Council (NSERC) of Canada for funding this work. P.W.S. thanks NSERC for a PGS D fellowship. Mes=2,4,6-trimethylphenyl.


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Unique pathway: The radical-initiated addition polymerization of MesP=CPh2 propagates through the ortho-bound CH3 group of the Mes moiety after C[BOND]H 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.