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Anion-π Catalysis on Carbon Nanotubes

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Bornhof, Anna Bea and Vázquez Nakagawa, M. and Rodríguez Pérez, Laura and Herranz, M.Angeles and Sakai, Naomi and Martín, Nazario and Matile, Stefan and López Andarias, Javier (2019) Anion-π Catalysis on Carbon Nanotubes. Angewandte chemie. International edition, 58 (45). pp. 16097-16100. ISSN 1433-7851

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Official URL: https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.201909540



Abstract

Induced π acidity from polarizability is currently emerging as most effective to stabilize anionic transition states on aromatic π surfaces, that is anion-π catalysis. To access extreme polarizability, we here propose a shift of attention from homogeneous toward heterogeneous anion-π catalysis on higher carbon allotropes. According to benchmark enolate addition chemistry, multi-walled carbon nanotubes equipped with tertiary amine bases outperform single-walled carbon nanotubes clearly. This difference is consistent with polarizability of the former not only along but also between the tubes. Inactivation by π-basic aromatics and saturation with increasing catalyst concentration support that catalysis occurs on the π surface of the tubes. Increasing rate and selectivity of existing anion-π catalysts (naphthalenediimides > fullerenes) on the Surface of unmodified nanotubes is consistent with transition-state stabilization by electron sharing into the tubes, i.e., induced anion-π interactions. On pristine tubes, anion-π catalysis is realized by noncovalent interfacing with π-basic pyrenes.


Item Type:Article
Uncontrolled Keywords:Anion-macrodipoleinteractions, anion–pcatalysis, carbonnanotubes, inducedpacidity, polarizability
Subjects:Sciences > Chemistry > Chemistry, Organic
ID Code:58520
Deposited On:14 Jan 2020 09:24
Last Modified:14 Jan 2020 11:17

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