Synthesis of Alternating trans-AB Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Alkylidenes
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Synthesis of alternating with SI.pdf
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Author(s)
Hoveyda, Amir H.
Jeong, Hyangsoo
John, Jeremy M
Schrock, Richard Royce
Date Issued
February 2015
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Jeong, Hyangsoo; John, Jeremy M.; Schrock, Richard R. and Hoveyda, Amir H. "Synthesis of Alternating trans-AB Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Alkylidenes." Journal of the American Chemical Society 137, no. 6 (February 2015): 2239–2242. © 2015 American Chemical Society (ACS)
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Author's final manuscript
Abstract
Four alternating AB copolymers have been prepared through ring-opening metathesis polymerization (ROMP) with Mo(NR)(CHCMe₂Ph)[OCMe(CF₃)₂]₂ initiators (R = 2,6-Me₂C₆H₃ (1) or 2,6-i-Pr₂C₆H₃ (2)). The A:B monomer pairs copolymerized by 1 are cyclooctene (A):2,3-dicarbomethoxy-7-isopropylidenenorbornadiene (B), cycloheptene (A′):dimethylspiro[bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate-7,1′-cyclopropane] (B′), A:B′, and A′:B; A′:B′ and A:B′ are also copolymerized by 2. The >90% poly(A-alt-B) copolymers are formed with heterodyads (AB) that have the trans configuration. Evidence suggests that one trans hetero C═C bond is formed when A (A or A′) reacts with the syn form of the alkylidene made from B (syn-MB = syn-MB or syn-MB′) to give anti-MA, while the other trans C═C bond is formed when B reacts with anti-MA to give syn-MB. Cis and trans AA dyads are proposed to arise when A reacts with anti-MA in competition with B reacting with anti-MA.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.5b00221
