Hexakis(4-(N-butylpyridylium))benzene: a six-electron organic redox system |
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Authors: | Han Zhenfu Vaid Thomas P Rheingold Arnold L |
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Institution: | Department of Chemistry and Center for Materials Innovation, Washington University, St. Louis, Missouri 63130, USA. |
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Abstract: | The cobalt-catalyzed cyclotrimerization of bis(4-pyridyl)acetylene affords hexakis(4-pyridyl)benzene in moderate yield. Alkylation with n-butyltriflate gives hexakis(4-(N-butylpyridylium))benzene triflate (1 6+), which can be reduced with Na/Hg in DMF to neutral 10. A single-crystal X-ray diffraction structure reveals that 1 0 has a chair-cyclohexane-like core and a 6]radialene structure. Cyclic voltammetry shows that 1 6+ is reversibly reduced to 1 2+ in one four-electron step and 1 2+ is reversibly reduced to 1 0 in one two-electron step. A reduction by four electrons at one potential is unprecedented for a molecule in which the electrochemically active centers are in electronic communication. The large structural transformation from 1 6+ to 1 0 is responsible for the "potential inversion" in the cyclic voltammetry, and DFT calculations suggest a possible structure for the stable intermediate 1 2+. A comparison is made to the electrochemistry and structural transformations in a previously prepared 4]radialene analogue of 1 0. |
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