RT Journal Article
T1 Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
A1 Lión Villar, Juan
A1 Torchon, Herdya S.
A1 Zhu, Yikun
A1 Wei, Zheing
A1 Fernández García, Jesús Manuel
A1 Fernández López, Israel
A1 Petrukhina, Marina A.
A1 Martín León, Nazario
AB The chemical reduction of a bilayer spironanographene, spiro-NG (C137H120), with Na and K metals in the presence of [2.2.2]cryptand to yield [Na+(2.2.2-cryptand)](C137H121−) (1) and [K+(2.2.2-cryptand)](C137H121−) (2), respectively, is reported. X-ray crystallography reveals the formation of a new “naked” anion (spiro-NGH−), in which spirocyclic ring cleavage and subsequent hydrogenation have occurred. Density Functional Theory (DFT) calculations suggest that the generation of the radical anion of the parent nanographene (spiro-NG•−), upon electron acceptance from Na and K metals, induces the cleavage of the strained spirobifluorene core. The resulting spin density localizes on a particular carbon atom, previously attached to the spiranic sp3 carbon atom, facilitating a site-specific hydrogenation to afford (spiro-NGH−). The electrostatic potential map of this anion reveals electron density concentrated at the five-membered ring of the readily formed indenyl fragment, thus enhancing the aromaticity of the system. Furthermore, nuclear magnetic resonance (NMR) and UV–vis absorption spectroscopy experiments allowed to follow the in situ reduction and hydrogenation processes in detail.
PB Wiley
YR 2025
FD 2025-06-23
LK https://hdl.handle.net/20.500.14352/123736
UL https://hdl.handle.net/20.500.14352/123736
LA eng
NO Lión‐Villar, Juan, et al. «Reduction‐Induced C─C Cleavage and Site‐Specific Hydrogenation of a Highly Strained Bilayer Spironanographene». Angewandte Chemie International Edition, vol. 64, n.o 33, agosto de 2025, p. e202510209. DOI.org (Crossref), https://doi.org/10.1002/anie.202510209.
NO Ministerio de Ciencia, Innovación y Universidades
NO Comunidad de Madrid
NO European Union
DS Docta Complutense
RD 8 abr 2026