Publications [#338392] of Stephen L Craig

Journal Articles

1. Sha, Y; Zhang, Y; Xu, E; Wang, Z; Zhu, T; Craig, SL; Tang, C, Quantitative and Mechanistic Mechanochemistry in Ferrocene Dissociation., ACS macro letters, vol. 7 no. 10 (October, 2018), pp. 1174-1179, American Chemical Society (ACS) [doi]
   (last updated on 2026/01/16)

   Abstract:
   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.