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

  • Identification data

    Identifier: imarina:9216316
    Authors:
    Hu, YajingYao, Yang-RongLiu, XuechenYu, AoXie, XiaomingAbella, LauraRodriguez-Fortea, AntonioPoblet, Josep MAkasaka, TakeshiPeng, PingZhang, QianyanXie, Su-YuanLi, Fang-FangLu, Xing
    Abstract:
    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.
  • Others:

    Author, as appears in the 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
    Department: Química Física i Inorgànica
    URV's Author/s: Abella Guzman, Laura / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
    Keywords: Isomers I-h-sc3n-at-c-80 Endohedral metallofullerenes Electrosynthesis Efficient Acid
    Abstract: 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.
    Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
    Author identifier: 0000-0002-4533-0623 0000-0001-5884-5629
    Record's date: 2024-10-12
    Journal volume: 12
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2021/SC/D1SC01178B#!divAbstract
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Chemical Science. 12 (23): 8123-8130
    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
    Article's DOI: 10.1039/d1sc01178b
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2021
    Publication Type: Journal Publications
  • Keywords:

    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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