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

We report here the polymerization of several 7-isopropylidene-2,3-disubstituted norbomadienes, 7-oxa-2,3-dicarboalkoxynorbornadienes, and 11-oxa-benzonorbornadienes with a single tungsten oxo alkylidene catalyst, W(O)(CH-t-Bu)(OHMT)(Me(2)Pyr) (OHMT = 2,6-dimesitylphenoxide; Me(2)Pyr = 2,5-dimethylpyrrolide) to give cis, stereoregular polymers. The tacticities of the menthyl ester derivatives of two polymers were determined 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 polymerized stereoregularly with W(O)(CHCMe2Ph)(Me(2)Pyr)(OHMT) alone, but a cis, stereoregular polymer was formed in the presence of 1 equiv of B(C6F5)(3).