Статья

Quantitative and Mechanistic Mechanochemistry in Ferrocene Dissociation

Ye ShaDepartment of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United StatesYudi ZhangDepartment of Chemistry, Duke University, Durham, North Carolina 27708, United StatesEnhua XuGraduate School of System Informatics, Kobe University, Kobe 657-8501, JapanZi WangDepartment of Chemistry, Duke University, Durham, North Carolina 27708, United StatesTianyu ZhuDepartment of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United StatesStephen L. CraigDepartment of Chemistry, Duke University, Durham, North Carolina 27708, United StatesChuanbing TangDepartment of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States

2018en

ABI

Аннотация

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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Идентификаторы

DOI: 10.1021/acsmacrolett.8b00625

Цитирования и источники

Цитирований: 2Использованных источников: 0

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