Publications [#370191] of Stephen L Craig

Journal Articles

  1. Wakefield, H; Kevlishvili, I; Wentz, KE; Yao, Y; Kouznetsova, TB; Melvin, SJ; Ambrosius, EG; Herzog-Arbeitman, A; Siegler, MA; Johnson, JA; Craig, SL; Kulik, HJ; Klausen, RS, "Synthesis and Ring-Opening Metathesis Polymerization of a Strained trans-Silacycloheptene and Single-Molecule Mechanics of Its Polymer.", Journal of the American Chemical SocietyMay,, 2023, 145(18), 10187-10196 [doi].
    (last updated on 2026/01/19)

    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.