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• W2023903985 endingPage "3322" @default.
• W2023903985 startingPage "3312" @default.
• W2023903985 abstract "Mechanistic features of the isoselective polymerization of styrene promoted by racemic allyl ansa-lanthanidocene complexes rac-{CMe2(Ind)2}Ln(allyl)(THF)n (Ind =5-indenyl; allyl = C3H5, n = 1, Ln = Y (1), Nd (2); allyl =1,3-(SiMe3)2C3H3, n = 0, Ln = Y (3), Nd (4)), which act as unique single-component catalysts, have been investigated by experimental and theoretical methods. Combined 1H NMR and MALDI−ToF−MS analyses conducted on low molecular weights isotactic polystyrene (iPS) produced by compounds 1 or 2 established the presence of allyl end-groups and therefore that polymerization is initiated by insertion of styrene into Ln−C(allyl). 1H, 2D, and 13C NMR analyses performed on H(D)-iPS-nBu polymers, selectively produced by coordinative chain transfer polymerization (CCTP) of styrene with the binary system 3/Mg(nBu)2 (1:10), evidenced that the polymerization is highly regioselective and proceeds in a secondary insertion mode, both in the initiation and propagation steps. Microstructural analyses of the backbone of crude (unfractionated) polymers produced with 1−4 evidenced a virtually perfect isoselective (mmmmmm > 0.99) polymerization up to 120 °C. Stereoerrors observed in the 13C{1H} NMR spectra of the iPS produced at 130 °C with 1−4 are consistent with an enantiomorphic site control operative during the polymerization. DFT computations of the first and second insertions of styrene in 3 confirmed the above features and the overall mechanistic scenario." @default.
• W2023903985 created "2016-06-24" @default.
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• W2023903985 date "2011-04-07" @default.
• W2023903985 modified "2023-10-14" @default.
• W2023903985 title "Isoselective Styrene Polymerization Catalyzed by <i>ansa</i>-Bis(indenyl) Allyl Rare Earth Complexes. Stereochemical and Mechanistic Aspects" @default.
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• W2023903985 doi "https://doi.org/10.1021/ma2003757" @default.
• W2023903985 hasPublicationYear "2011" @default.
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