Quantitative and Mechanistic Mechanochemistry in Ferrocene Dissociation.


Journal Article

Ferrocene is classically regarded as being highly inert owing to the large dissociation energy of metal-cyclopentadienyl (Cp) bonds. We show that the Fe-Cp bond in ferrocene is the preferential site of mechanochemical scission in the pulsed ultrasonication of main-chain ferrocene-containing polybutadiene-derived polymers. Quantitative studies reveal that the Fe-Cp bond is similar in strength to the carbon-nitrogen bond of an azobisdialkylnitrile (bond dissociation energy < -0 kcal/mol), despite the significantly higher Fe-Cp bond dissociation energy (approximately 90 kcal/mol). Mechanistic studies are consistent with a predominately heterolytic mechanism of chain scission. DFT calculations provide insights into the origins of ferrocene's mechanical lability.

Full Text

Duke Authors

Cited Authors

  • Sha, Y; Zhang, Y; Xu, E; Wang, Z; Zhu, T; Craig, SL; Tang, C

Published Date

  • October 2018

Published In

Volume / Issue

  • 7 / 10

Start / End Page

  • 1174 - 1179

PubMed ID

  • 31098336

Pubmed Central ID

  • 31098336

Electronic International Standard Serial Number (EISSN)

  • 2161-1653

International Standard Serial Number (ISSN)

  • 2161-1653

Digital Object Identifier (DOI)

  • 10.1021/acsmacrolett.8b00625


  • eng