Isomerization Polymerization of the Phosphaalkene MesPCPh₂: An Alternative Microstructure for Poly(methylenephosphine)s

Abstract

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