Mechanochemistry of Cubane.

Journal Article (Journal Article)

We report the mechanochemical reactivity of the highly strained pentacyclic hydrocarbon cubane. The mechanical reactivity of cubane is explored for three regioisomers with 1,2-, 1,3-, and 1,4-substituted pulling attachments. Whereas all compounds can be activated thermally, mechanical activation is observed via pulsed ultrasonication of cubane-containing polymers only when force is applied via 1,2-attachment. The single observed product of the force-coupled reaction is a thermally inaccessible syn -tricyclooctadiene, in contrast to cyclooctatetraene (observed thermally) or a pair of cyclobutadienes that would result from sequential cyclobutane scission. We further quantify the mechanochemical reactivity of cubane by single molecule force spectroscopy, and force-coupled rate constants for ring opening reach ∼33 s-1 at a force of ∼1.55 nN, lower than forces of 1.8-2.0 nN that are typical of conventional cyclobutanes.

Full Text

Duke Authors

Cited Authors

  • Wang, L; Zheng, X; Kouznetsova, TB; Yen, T; Ouchi, T; Brown, CL; Craig, SL

Published Date

  • December 2022

Published In

Volume / Issue

  • 144 / 50

Start / End Page

  • 22865 - 22869

PubMed ID

  • 36479874

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/jacs.2c10878


  • eng