Articles producció científica> Química Física i Inorgànica

Unexpected formation of 1,2-and 1,4-bismethoxyl Sc3N@I-h-C-80 derivatives via regioselective anion addition: an unambiguous structural identification and mechanism study

  • Dades identificatives

    Identificador: imarina:9216316
    Autors:
    Hu, YajingYao, Yang-RongLiu, XuechenYu, AoXie, XiaomingAbella, LauraRodriguez-Fortea, AntonioPoblet, Josep MAkasaka, TakeshiPeng, PingZhang, QianyanXie, Su-YuanLi, Fang-FangLu, Xing
    Resum:
    An attempt to achieve heterocyclic cycloadducts of Sc3N@I-h-C-80 via reaction with Ph2C=O, PhC equivalent to CPh or PhC equivalent to N in the presence of tetrabutylammonium hydroxide (TBAOH) stored in CH3OH led to the formation of the unexpected bismethoxyl adducts of Sc3N@I-h-C-80 (1 and 2). Further studies reveal that TBAOH in CH3OH can boost the CH3O- addition efficiently, regardless of the presence of other reagents. Single-crystal X-ray diffraction results firmly assign the molecular structures of 1 and 2 as respective 1,4- and 1,2-bismethoxyl adducts, and reveal unusual relationships between the internal Sc3N cluster and the addition modes, in addition to the unusual packing mode in view of the orientation of the methoxyl groups. Electrochemical results demonstrate smaller electrochemical gaps for 1 and 2, relative to that of Sc3N@I-h-C-80, confirming their better electroactive properties. Finally, a plausible reaction mechanism involving anion addition and a radical reaction was proposed, presenting new insights into the highly selective reactions between the methoxyl anion and metallofullerenes. 1 and 2 represent the first examples of methoxyl derivatives of metallofullerenes. This work not only presents a novel and facile strategy for the controllable synthesis of alkoxylated metallofullerene derivatives, but also provides new non-cycloadducts for the potential applications of EMFs.
  • Altres:

    Autor segons l'article: Hu, Yajing; Yao, Yang-Rong; Liu, Xuechen; Yu, Ao; Xie, Xiaoming; Abella, Laura; Rodriguez-Fortea, Antonio; Poblet, Josep M; Akasaka, Takeshi; Peng, Ping; Zhang, Qianyan; Xie, Su-Yuan; Li, Fang-Fang; Lu, Xing
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Abella Guzman, Laura / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
    Paraules clau: Isomers I-h-sc3n-at-c-80 Endohedral metallofullerenes Electrosynthesis Efficient Acid
    Resum: An attempt to achieve heterocyclic cycloadducts of Sc3N@I-h-C-80 via reaction with Ph2C=O, PhC equivalent to CPh or PhC equivalent to N in the presence of tetrabutylammonium hydroxide (TBAOH) stored in CH3OH led to the formation of the unexpected bismethoxyl adducts of Sc3N@I-h-C-80 (1 and 2). Further studies reveal that TBAOH in CH3OH can boost the CH3O- addition efficiently, regardless of the presence of other reagents. Single-crystal X-ray diffraction results firmly assign the molecular structures of 1 and 2 as respective 1,4- and 1,2-bismethoxyl adducts, and reveal unusual relationships between the internal Sc3N cluster and the addition modes, in addition to the unusual packing mode in view of the orientation of the methoxyl groups. Electrochemical results demonstrate smaller electrochemical gaps for 1 and 2, relative to that of Sc3N@I-h-C-80, confirming their better electroactive properties. Finally, a plausible reaction mechanism involving anion addition and a radical reaction was proposed, presenting new insights into the highly selective reactions between the methoxyl anion and metallofullerenes. 1 and 2 represent the first examples of methoxyl derivatives of metallofullerenes. This work not only presents a novel and facile strategy for the controllable synthesis of alkoxylated metallofullerene derivatives, but also provides new non-cycloadducts for the potential applications of EMFs.
    Àrees temàtiques: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
    Identificador de l'autor: 0000-0002-4533-0623 0000-0001-5884-5629
    Data d'alta del registre: 2024-10-12
    Volum de revista: 12
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    Enllaç font original: https://pubs.rsc.org/en/content/articlelanding/2021/SC/D1SC01178B#!divAbstract
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Chemical Science. 12 (23): 8123-8130
    Referència de l'ítem segons les normes APA: Hu, Yajing; Yao, Yang-Rong; Liu, Xuechen; Yu, Ao; Xie, Xiaoming; Abella, Laura; Rodriguez-Fortea, Antonio; Poblet, Josep M; Akasaka, Takeshi; Peng, Pi (2021). Unexpected formation of 1,2-and 1,4-bismethoxyl Sc3N@I-h-C-80 derivatives via regioselective anion addition: an unambiguous structural identification and mechanism study. Chemical Science, 12(23), 8123-8130. DOI: 10.1039/d1sc01178b
    DOI de l'article: 10.1039/d1sc01178b
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2021
    Tipus de publicació: Journal Publications
  • Paraules clau:

    Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Isomers
    I-h-sc3n-at-c-80
    Endohedral metallofullerenes
    Electrosynthesis
    Efficient
    Acid
    Química
    Materiais
    Interdisciplinar
    General chemistry
    Farmacia
    Ciências biológicas iii
    Ciências biológicas i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Astronomia / física
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