標題: Evolution of Late Transition-Metal-Catalyzed Intermolecular Reductive Coupling Reaction of [60]Fullerene and N-Sulfonylaldimines: Competing Formation of Hydrobenzylated [60]Fullerenes and 1,2-Dihydrofullerene
作者: Rajeshkumar, Venkatachalam
Chuang, Shih-Ching
應用化學系
Department of Applied Chemistry
關鍵字: Fullerenes;Transition metals;C-C coupling;Reductive coupling
公開日期: 1-七月-2012
摘要: A system based on late transition-metal halides, phosphanes, water, and reducing agents in 1,2-dichlorobenzene can efficiently catalyze the intermolecular reductive coupling of [60]fullerene with N-sulfonylaldimines to afford novel 1,2-hydrobenzylated [60]fullerene derivatives. We found that both group VII?B metals (cobalt, rhodium, iridium) and group VIII?B metals (nickel, palladium, platinum) perform this coupling reaction. A control experiment in the absence of aldimines produced C60H2, which showed that the reaction might proceed via a [60]fullerene metal complex [M(?2-C60)(ligand)]. An isotope labeling experiment with D2O as deuterium source resulted in deuterioaryzilation with deuterium bonded to the sp3-carbon of C60, providing evidence of a five-membered azametallacycle intermediate. Evaluation of the scope of reductive coupling reaction with versatile aldimines gave access to the hydroaryzilation products. All the reductive coupling products were completely characterized by IR and NMR spectroscopy and ESI mass spectrometry. A possible reaction mechanism based on these results is proposed. This discovery of the formation of reductive coupling compounds and metal-catalyzed formation of C60H2 are both new to metal catalysis and fullerene chemistry.
URI: http://hdl.handle.net/11536/16441
ISSN: 1434-193X
期刊: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Volume: 
Issue: 20
結束頁: 3795
顯示於類別:期刊論文


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