13C NMR spectra of tactic and atactic hydrogenated ring-opened polymers of enantiomeric and racemic endo,exo-5,6-dimethylnorbornene
โ Scribed by Kenneth J. Ivin; Alan M. Kenwright; Gretchen E. Hofmeister; David H. McConville; Richard R. Schrock; Valia Amir-Ebrahimir; Andrew G. Carvill; James G. Hamilton; John J. Rooney
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 442 KB
- Volume
- 199
- Category
- Article
- ISSN
- 1022-1352
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โฆ Synopsis
Polymers 1 of the title monomer, prepared using well-defined molybdenum carbene complexes as catalysts, have been hydrogenated and the structures of the resultant polymers 2 examined by I3C NMR spectroscopy. The hydrogenated polymer made from the all-cis isotactic polymer of (+)-monomer showed a single set of I3C NMR lines as expected for an NX sequence of endo (N) and ex0 (X) substituents. The hydrogenated polymer made from a cis isotactic polymer of (+)-monomer showed additional fine structure arising from the random incorporation of both enantiomers in the isotactic polymer chain: four equal lines for C-9 (orientational triad sensitivity), two equal lines for C-3, C-4, C-5, and C-1 (dyad sensitivity), but single lines for C-8, C-2, C-7 and C-6 (insensitive to the relative orientation of adjacent repeating units). The hydrogenated polymer made from a trans atactic polymer of (+)-monomer showed fine structure due to the presence of both m and r dyads. That made from a trans atactic polymer of (+)-monomer contains 16 possible triad sequences and gave a more complicated spectrum. A complete assignment was made for the first three polymers and a partial assignment for the fourth. Polymers made using non-carbene catalysts were also examined. Hydrogenation of an all-trans precursor made from (+)-monomer using RuC13 as catalyst gave an atactic polymer, confirming previous observations. Hydrogenation of a 6 1 % cis, cis/trans blocky precursor, made from (+)-monomer using OsC13PhC X H as catalyst, gave a syndiotactic-biased stereoblocky polymer, indicating a c/r, t/m correlation in the precursor polymer.
๐ SIMILAR VOLUMES
13C NMR spectra of the three title polymers have been determined for polymers of different tacticities. Assignments to the various possible HWHT/TT and m/r dyad structures were made. These were facilitated by the use of optically active monomers in the case of 1 and 3. In the precursor polymers the