Synthesis and Ring-Opening Metathesis Polymerization of a Strained trans-Silacycloheptene and Single-Molecule Mechanics of Its Polymer
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10405303.pdf
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Author(s)
Wakefield, Herbert
Kevlishvili, Ilia
Wentz, Kelsie E
Yao, Yunxin
Kouznetsova, Tatiana B
Melvin, Sophia J
Ambrosius, Em G
Herzog-Arbeitman, Abraham
Siegler, Maxime A
Johnson, Jeremiah A
Date Issued
April 5, 2023
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Synthesis and Ring-Opening Metathesis Polymerization of a Strained trans-Silacycloheptene and Single-Molecule Mechanics of Its Polymer. Herbert Wakefield IV, Ilia Kevlishvili, Kelsie E. Wentz, Yunxin Yao, Tatiana B. Kouznetsova, Sophia J. Melvin, Em G. Ambrosius, Abraham Herzog-Arbeitman, Maxime A. Siegler, Jeremiah A. Johnson, Stephen L. Craig, Heather J. Kulik, and Rebekka S. Klausen. Journal of the American Chemical Society 2023 145 (18), 10187-10196.
Version
Author's final manuscript
Abstract
The cis- and trans-isomers of a silacycloheptene were selectively synthesized by the alkylation of a silyl dianion, a novel approach to strained cycloalkenes. The trans-silacycloheptene (trans-SiCH) was significantly more strained than the cis isomer, as predicted by quantum chemical calculations and confirmed by crystallographic signatures of a twisted alkene. Each isomer exhibited distinct reactivity toward ring-opening metathesis polymerization (ROMP), where only trans-SiCH afforded high-molar-mass polymer under enthalpy-driven ROMP. Hypothesizing that the introduction of silicon might result in increased molecular compliance at large extensions, we compared poly(trans-SiCH) to organic polymers by single-molecule force spectroscopy (SMFS). Force-extension curves from SMFS showed that poly(trans-SiCH) is more easily overstretched than two carbon-based analogues, polycyclooctene and polybutadiene, with stretching constants that agree well with the results of computational simulations.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.3c01004
