Formation of Alternating trans - A - alt - B Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Imido Alkylidene Complexes

Jeong, Hyangsoo; John, Jeremy M.; Schrock, Richard R.

doi:10.1021/acs.organomet.5b00709

Title: Formation of Alternating trans - A - alt - B Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Imido Alkylidene Complexes

Journal Article · Tue Oct 13 00:00:00 EDT 2015 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.5b00709· OSTI ID:1557792

Jeong, Hyangsoo ^[1]; John, Jeremy M. ^[1]; Schrock, Richard R. ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Ring-opening metathesis polymerization (ROMP) is enabled to prepare trans-poly(A-alt-B) polymers from a 1:1 mixture of A and B where A is a cyclic olefin such as cyclooctene (A₁) or cycloheptene (A₂) and B is a large norbornadiene or norbornene derivative such as 2,3-dicarbomethoxy-7-isopropylidenenorbornadiene (B₁) or dimethylspirobicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate-7,1'-cyclopropane (B₂). The most successful initiators that were examined are of the type Mo(NR)(CHCMe₂Ph)[OCMe(CF₃)₂]₂ (R = 2,6-Me₂C₆H₃ (1) or 2,6-i-Pr₂C₆H₃ (2)). The trans configuration of the AB linkages is proposed to result from the steric demand of B. Both anti-MB and syn-MB alkylidenes are observed during the copolymerization, where B was last inserted into a Mo=C bond, although anti-MB dominates as the reaction proceeds. anti-MB is lower in energy than syn-MB, does not react readily with eitherA or B, and interconverts slowly with syn-MB through rotation about the Mo=C bond. Syn-MB does not readily react with B, but it does react slowly with A (rate constant ~1 M^–1 s^–1) to give anti-MA and one trans-AB linkage. anti-MA then reacts with B (rate constant ~300 M^–1 s^–1 or larger) to give syn-MB and the second trans-AB linkage. The reaction has been modeled using experimental data in order to obtain the estimated rate constants above. The reaction between anti-MA and A is presented to give rise to AA linkages, but AA dyads can amount to <5%. Several other A and B monomers, initiators, and conditions were researched.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-86ER13564

OSTI ID:: 1557792

Journal Information:: Organometallics, Vol. 34, Issue 20; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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