Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators
We report here the polymerization 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-dimethylpyrro...
| Main Authors: | , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2016
|
| Online Access: | http://hdl.handle.net/1721.1/104039 https://orcid.org/0000-0002-7405-6811 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1826214118552502272 |
|---|---|
| author | Forrest, William P. Weis, Jonathan Garrett John, Jeremy M. Axtell, Jonathan Simpson, Jeffrey H. Swager, Timothy M. Schrock, Richard Royce |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Forrest, William P. Weis, Jonathan Garrett John, Jeremy M. Axtell, Jonathan Simpson, Jeffrey H. Swager, Timothy M. Schrock, Richard Royce |
| author_sort | Forrest, William P. |
| collection | MIT |
| description | We report here the polymerization 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 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)(Me2Pyr)(OHMT) alone, but a cis, stereoregular polymer was formed in the presence of 1 equiv of B(C6F5)3. |
| first_indexed | 2024-09-23T15:59:47Z |
| format | Article |
| id | mit-1721.1/104039 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:59:47Z |
| publishDate | 2016 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1040392022-09-29T17:36:40Z Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators Forrest, William P. Weis, Jonathan Garrett John, Jeremy M. Axtell, Jonathan Simpson, Jeffrey H. Swager, Timothy M. Schrock, Richard Royce Massachusetts Institute of Technology. Department of Chemistry Forrest, William P. Weis, Jonathan Garrett John, Jeremy M. Axtell, Jonathan Simpson, Jeffrey H. Swager, Timothy M. Schrock, Richard Royce We report here the polymerization 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 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)(Me2Pyr)(OHMT) alone, but a cis, stereoregular polymer was formed in the presence of 1 equiv of B(C6F5)3. United States. Dept. of Energy (DE-FG02- 86ER13564) Defense Threat Reduction Agency (DTRA) (Chemical and Biological Technologies, grant BA12PHM123 in the “Dynamic Multifunctional Materials for a Second Skin D[MS]2” program) 2016-08-26T17:14:33Z 2016-08-26T17:14:33Z 2014-07 2014-06 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/104039 "Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators." Journal of the American Chemical Society 136:31 (2014) , pp. 10910-10913. © 2014 American Chemical Society. https://orcid.org/0000-0002-7405-6811 https://orcid.org/0000-0001-5827-3552 en_US http://dx.doi.org/10.1021/ja506446n Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Forrest, William P. Weis, Jonathan Garrett John, Jeremy M. Axtell, Jonathan Simpson, Jeffrey H. Swager, Timothy M. Schrock, Richard Royce Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators |
| title | Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators |
| title_full | Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators |
| title_fullStr | Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators |
| title_full_unstemmed | Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators |
| title_short | Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators |
| title_sort | stereospecific ring opening metathesis polymerization of norbornadienes employing tungsten oxo alkylidene initiators |
| url | http://hdl.handle.net/1721.1/104039 https://orcid.org/0000-0002-7405-6811 https://orcid.org/0000-0001-5827-3552 |
| work_keys_str_mv | AT forrestwilliamp stereospecificringopeningmetathesispolymerizationofnorbornadienesemployingtungstenoxoalkylideneinitiators AT weisjonathangarrett stereospecificringopeningmetathesispolymerizationofnorbornadienesemployingtungstenoxoalkylideneinitiators AT johnjeremym stereospecificringopeningmetathesispolymerizationofnorbornadienesemployingtungstenoxoalkylideneinitiators AT axtelljonathan stereospecificringopeningmetathesispolymerizationofnorbornadienesemployingtungstenoxoalkylideneinitiators AT simpsonjeffreyh stereospecificringopeningmetathesispolymerizationofnorbornadienesemployingtungstenoxoalkylideneinitiators AT swagertimothym stereospecificringopeningmetathesispolymerizationofnorbornadienesemployingtungstenoxoalkylideneinitiators AT schrockrichardroyce stereospecificringopeningmetathesispolymerizationofnorbornadienesemployingtungstenoxoalkylideneinitiators |