Quantitative and Mechanistic Mechanochemistry in Ferrocene Dissociation.
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.
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- 3406 Physical chemistry
- 3403 Macromolecular and materials chemistry
- 0306 Physical Chemistry (incl. Structural)
- 0303 Macromolecular and Materials Chemistry
Citation
Published In
DOI
EISSN
ISSN
Publication Date
Volume
Issue
Start / End Page
Related Subject Headings
- 3406 Physical chemistry
- 3403 Macromolecular and materials chemistry
- 0306 Physical Chemistry (incl. Structural)
- 0303 Macromolecular and Materials Chemistry