Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene

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 “...

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Autores: Lión Villar, Juan, Torchon, Herdya S., Zhu, Yikun, Wei, Zheing, Fernández García, Jesús Manuel, Fernández López, Israel, Petrukhina, Marina A., Martín León, Nazario
Formato: artículo
Fecha de publicación:2025
País:España
Recursos:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/123736
Acesso em linha:https://hdl.handle.net/20.500.14352/123736
Access Level:acceso abierto
Palavra-chave:547
Química
2306 Química Orgánica
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spelling Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer SpironanographeneLión Villar, JuanTorchon, Herdya S.Zhu, YikunWei, ZheingFernández García, Jesús ManuelFernández López, IsraelPetrukhina, Marina A.Martín León, Nazario547Química2306 Química OrgánicaThe 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.WileyUniversidad Complutense de Madrid20252025-06-2320252025-06-23journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/123736reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2022-139318NB-I00 ENTENDIENDO LOS FACTORES QUE CONTROLAN LA REACTIVIDAD EN GRUPOS PRINCIPALESAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2022-139318NB-I00 ENTENDIENDO LOS FACTORES QUE CONTROLAN LA REACTIVIDAD EN GRUPOS PRINCIPALESopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1237362026-06-02T12:44:21Z
dc.title.none.fl_str_mv Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
title Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
spellingShingle Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
Lión Villar, Juan
547
Química
2306 Química Orgánica
title_short Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
title_full Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
title_fullStr Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
title_full_unstemmed Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
title_sort Reduction-Induced C─C Cleavage and Site-Specific Hydrogenation of a Highly Strained Bilayer Spironanographene
dc.creator.none.fl_str_mv Lión Villar, Juan
Torchon, Herdya S.
Zhu, Yikun
Wei, Zheing
Fernández García, Jesús Manuel
Fernández López, Israel
Petrukhina, Marina A.
Martín León, Nazario
author Lión Villar, Juan
author_facet Lión Villar, Juan
Torchon, Herdya S.
Zhu, Yikun
Wei, Zheing
Fernández García, Jesús Manuel
Fernández López, Israel
Petrukhina, Marina A.
Martín León, Nazario
author_role author
author2 Torchon, Herdya S.
Zhu, Yikun
Wei, Zheing
Fernández García, Jesús Manuel
Fernández López, Israel
Petrukhina, Marina A.
Martín León, Nazario
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 547
Química
2306 Química Orgánica
topic 547
Química
2306 Química Orgánica
description 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.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025-06-23
2025
2025-06-23
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/123736
url https://hdl.handle.net/20.500.14352/123736
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2022-139318NB-I00 ENTENDIENDO LOS FACTORES QUE CONTROLAN LA REACTIVIDAD EN GRUPOS PRINCIPALES
Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023 PID2022-139318NB-I00 ENTENDIENDO LOS FACTORES QUE CONTROLAN LA REACTIVIDAD EN GRUPOS PRINCIPALES
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.812429

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