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Intramolecular coordination of the metal ion by the penultimate pyridine nitrogen is highly unlikely in the poly(3-methyl-2-vinylpyridine) system as a result of the steric hindrance due the penultimate 3′-methyl group and has been demonstrated by studying the stereochemistry of methylation of 1-lithio-1-(2-pyridyl)-3-(3′-methylpyridyl)-butane. See: Mathis, C.; Hogen-Esch, T. E., J. Am Chem. Soc., 1982, 104, 634.
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With regards to a question raised by a reviewer, 3-methyl-4-vinylpyridine was selected over 3-methyl-2-vinylpyridine because this monomer may be polymerized with lithium amides in toluene. This has to do with the increased stability of the anion generated from the 3-methyl-4-vinylpyridine. Both monomers are polymerizable by n-BuLi in THF. Additionally, studies are available which report the initiation of 4-vinylpyridine by soft enolate anions, successful initiation of 2-vinylpyridine by such soft anions is not known. See: (a) Schulz, R. C. Makromol. Chem., Macromol. Symp. 1990, 33, 1. (b) Li, J.; Khan, I. M. Makromol. Chem. 1991, 192, 3043.
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