Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators.

TitleStereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators.
Publication TypeJournal Article
Year of Publication2014
AuthorsForrest, WP, Weis, JG, John, JM, Axtell, JC, Simpson, JH, Swager, TM, Schrock, RR
JournalJournal of the American Chemical Society
Volume136
Pagination10910–10913
ISSN0002-7863
Keywordsnorbornadiene polymn tungsten oxo alkylidene catal
Abstract

We report here the polymn. of several 7-isopropylidene-2,3-disubstituted norbornadienes, 7-oxa-2,3-dicarboalkoxynorbornadienes, and 11-oxa-benzonorbornadienes with a single tungsten oxo alkylidene catalyst, W(O)(CH-t-Bu)(OHMT)(Me2Pyr) (OHMT = 2,6-dimesitylphenoxide; Me2Pyr = 2,5-dimethylpyrrolide) to give cis, stereoregular polymers. The tacticities of the menthyl ester derivs. of two polymers were detd. for two types. For poly(7-isopropylidene-2,3-dicarbomenthoxynorbornadiene) the structure was shown to be cis, isotactic, while for poly(7-oxa-2,3-dicarbomenthoxynorbornadiene) the structure was shown to be cis, syndiotactic. A bis-trifluoromethyl-7-isopropylidene norbornadiene was not polymd. stereoregularly with W(O)(CHCMe2Ph)(Me2Pyr)(OHMT) alone, but a cis, stereoregular polymer was formed in the presence of 1 equiv of B(C6F5)3. [on SciFinder(R)]

DOI10.1021/ja506446n