85320-16-7Relevant articles and documents
An Addition-Isomerization Mechanism for the Anionic Polymerization of MesP=CPh2 and m -XylP=CPh2
Rawe, Benjamin W.,Priegert, Andrew M.,Wang, Shuai,Schiller, Carl,Gerke, Sonja,Gates, Derek P.
, p. 2621 - 2629 (2018)
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, a -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 (or C-D) activation as the rate-determining step. This C-H activation step was modeled using DFT computations which revealed that the intramolecular proton transfer from the o-CH3 of the Mes moiety to the -CPh2 moiety has an activation energy (Ea = +18.5 kcal mol-1). For comparison, this computational value was quite close to the experimentally measured activation energy of propagation ArP=CPh2 in THF [Ea = 14.0 ± 0.9 kcal mol-1 (1a), 15.6 ± 2.8 kcal mol-1 (1b)].