Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators
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Schrock_Stereospecific ring with SI.pdf
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Author(s)
Autenrieth, Benjamin
Schrock, Richard Royce
Date Issued
April 2015
Journal
Macromolecules
Publisher
American Chemical Society (ACS)
Citation
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.
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Author's final manuscript
Abstract
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).
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/acs.macromol.5b00161
