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• W2794663670 abstract "We report that the anionic polymerization of P-mesityl and m-xylyl-substituted phosphaalkenes follows an unusual addition–isomerization mechanism. Specifically, the polymerization of ArP═CPh2 [Ar = Mes (1a), m-Xyl (1b)] involves the hindered nucleophilic anion intermediate, Ⓟ–P(Ar)–CPh2–, which undergoes a proton migration from the o-CH3 of the Mes/m-Xyl moiety to the −CPh2 moiety to afford a propagating benzylic anion. This mechanism is supported by the preparation of model compounds MeP(CHPh2)-4,6-Me2C6H2–2-CH2–CPh3 (2a) or MeP(CHPh2)-6-MeC6H3–2-CH2–CPh3 (2b), which were both crystallographically characterized. Polymerization of 1a or 1b in THF solution using n-BuLi (2 mol %) revealed 1H and 13C NMR signals assigned to −CH2– and −CHPh2 groups consistent with an addition–isomerization polymerization mechanism to afford poly(methylenephosphine) 3a or 3b. A large kinetic isotope effect (≤23) was determined for the n-BuLi-initiated polymerization of 1a-d9 compared to 1a in THF at 50 °C, consistent with C–H ..." @default.
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• W2794663670 date "2018-03-27" @default.
• W2794663670 modified "2023-10-17" @default.
• W2794663670 title "An Addition–Isomerization Mechanism for the Anionic Polymerization of MesP═CPh₂ and <i>m</i>-XylP═CPh₂" @default.
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• W2794663670 doi "https://doi.org/10.1021/acs.macromol.8b00100" @default.
• W2794663670 hasPublicationYear "2018" @default.
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