RT Journal Article
T1 Anion-π Catalysis on Carbon Nanotubes
A1 Bornhof, Anna Bea
A1 Vázquez Nakagawa, M.
A1 Rodríguez Pérez, Laura
A1 Herranz, M.Angeles
A1 Sakai, Naomi
A1 Martín, Nazario
A1 Matile, Stefan
A1 López Andarias, Javier
AB 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.
PB Wiley-VCH
SN 1433-7851
YR 2019
FD 2019-11
LK https://hdl.handle.net/20.500.14352/5994
UL https://hdl.handle.net/20.500.14352/5994
LA eng
NO Ministerio de Ciencia e Innovación (MICINN)
NO Comunidad de Madrid
DS Docta Complutense
RD 10 abr 2025