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| - Hexakis(4-(N-butylpyridylium))benzene: A Six-Electron OrganicRedox System
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| - The cobalt-catalyzed cyclotrimerization of bis(4-pyridyl)acetylene affords hexakis(4-pyridyl)benzene inmoderate yield. Alkylation with n-butyltriflate gives hexakis(4-(N-butylpyridylium))benzene triflate (16+),which can be reduced with Na/Hg in DMF to neutral 10. A single-crystal X-ray diffraction structurereveals that 10 has a chair-cyclohexane-like core and a [6]radialene structure. Cyclic voltammetry showsthat 16+ is reversibly reduced to 12+ in one four-electron step and 12+ is reversibly reduced to 10 in onetwo-electron step. A reduction by four electrons at one potential is unprecedented for a molecule inwhich the electrochemically active centers are in electronic communication. The large structuraltransformation from 16+ to 10 is responsible for the “potential inversion” in the cyclic voltammetry, andDFT calculations suggest a possible structure for the stable intermediate 12+. A comparison is made tothe electrochemistry and structural transformations in a previously prepared [4]radialene analogue of 10.
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