Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators
We report the synthesis of >98% cis,isotactic and cis,syndiotactic polynorbornene (poly(NBE)) and poly(endo,anti-tetracyclododecene) (poly(TCD)). Cis,isotactic poly(NBE) and poly(TCD) were prepared employing Mo-based biphenolate imido alkylidene initiators, Mo(NR)(CHCMe[subscript 2]Ph)(Biphen) (B...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2017
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| Online Access: | http://hdl.handle.net/1721.1/108575 https://orcid.org/0000-0001-5827-3552 |
| _version_ | 1826201634036776960 |
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| author | Autenrieth, Benjamin Schrock, Richard Royce |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Autenrieth, Benjamin Schrock, Richard Royce |
| author_sort | Autenrieth, Benjamin |
| collection | MIT |
| description | We report the synthesis of >98% cis,isotactic and cis,syndiotactic polynorbornene (poly(NBE)) and poly(endo,anti-tetracyclododecene) (poly(TCD)). Cis,isotactic poly(NBE) and poly(TCD) were prepared employing Mo-based biphenolate imido alkylidene initiators, Mo(NR)(CHCMe[subscript 2]Ph)(Biphen) (Biphen = e.g., 3,3′-(t-Bu)[subscript 2]-5,5′-6,6′-(CH[subscript 3])[subscript 4]-1,1′-biphenyl-2,2′-diolate), while cis,syndiotactic poly(NBE) and poly(TCD) were prepared employing W-based imido or oxo monoaryloxide pyrrolide (MAP) initiators, W(X)(CHR′)(Pyrrolide)(OTer) (X = NR or O; OTer = a 2,6-terphenoxide). Addition of 1-hexene or coordinating solvents such as THF do not decrease the stereospecificity of the polymerization. Cis,iso and cis,syndio dyads can be distinguished through examination of [superscript 1]H and [superscript 13]C NMR spectra of the two polymers in a mixture. The polymers were hydrogenated to give isotactic and syndiotactic H-poly(NBE) and H-poly(TCD). |
| first_indexed | 2024-09-23T11:54:25Z |
| format | Article |
| id | mit-1721.1/108575 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:54:25Z |
| publishDate | 2017 |
| publisher | American Chemical Society (ACS) |
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| spelling | mit-1721.1/1085752022-10-01T06:53:19Z Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators Autenrieth, Benjamin Schrock, Richard Royce Massachusetts Institute of Technology. Department of Chemistry Schrock, Richard Royce Autenrieth, Benjamin Schrock, Richard Royce We report the synthesis of >98% cis,isotactic and cis,syndiotactic polynorbornene (poly(NBE)) and poly(endo,anti-tetracyclododecene) (poly(TCD)). Cis,isotactic poly(NBE) and poly(TCD) were prepared employing Mo-based biphenolate imido alkylidene initiators, Mo(NR)(CHCMe[subscript 2]Ph)(Biphen) (Biphen = e.g., 3,3′-(t-Bu)[subscript 2]-5,5′-6,6′-(CH[subscript 3])[subscript 4]-1,1′-biphenyl-2,2′-diolate), while cis,syndiotactic poly(NBE) and poly(TCD) were prepared employing W-based imido or oxo monoaryloxide pyrrolide (MAP) initiators, W(X)(CHR′)(Pyrrolide)(OTer) (X = NR or O; OTer = a 2,6-terphenoxide). Addition of 1-hexene or coordinating solvents such as THF do not decrease the stereospecificity of the polymerization. Cis,iso and cis,syndio dyads can be distinguished through examination of [superscript 1]H and [superscript 13]C NMR spectra of the two polymers in a mixture. The polymers were hydrogenated to give isotactic and syndiotactic H-poly(NBE) and H-poly(TCD). United States. Department of Energy (grant DE-FG0286ER13564) 2017-05-02T15:08:16Z 2017-05-02T15:08:16Z 2015-04 2015-03 Article http://purl.org/eprint/type/JournalArticle 0024-9297 1520-5835 http://hdl.handle.net/1721.1/108575 Autenrieth, Benjamin, and Richard R. Schrock. “Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators.” Macromolecules 48, no. 8 (April 28, 2015): 2493–2503. https://orcid.org/0000-0001-5827-3552 en_US http://pubs.acs.org/doi/abs/10.1021/acs.macromol.5b00161 Macromolecules 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) Prof. Schrock |
| spellingShingle | Autenrieth, Benjamin Schrock, Richard Royce Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators |
| title | Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators |
| title_full | Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators |
| title_fullStr | Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators |
| title_full_unstemmed | Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators |
| title_short | Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators |
| title_sort | stereospecific ring opening metathesis polymerization romp of norbornene and tetracyclododecene by mo and w initiators |
| url | http://hdl.handle.net/1721.1/108575 https://orcid.org/0000-0001-5827-3552 |
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