Počet záznamů: 1

Polymethylated [Fe(eta(6)-arene)(2)](2+) dications: methyl-group rearrangements and application of the EINS mechanism

  1. 1.
    0360469 - UACH-T 2012 RIV GB eng J - Článek v odborném periodiku
    Štíbr, Bohumil - Bakardjiev, Mario - Hájková, Zuzana - Holub, Josef - Padělková, Z. - Růžička, A. - Kennedy, J.D.
    Polymethylated [Fe(eta(6)-arene)(2)](2+) dications: methyl-group rearrangements and application of the EINS mechanism.
    Dalton Transactions. Roč. 40, č. 22 (2011), s. 5916-5920 ISSN 1477-9226
    Grant CEP: GA MŠk LC523
    Výzkumný záměr: CEZ:AV0Z40320502
    Klíčová slova: electrophile-induced nucleophilic substitution
    Kód oboru RIV: CA - Anorganická chemie
    Impakt faktor: 3.838, rok: 2011

    Reactions between the methylated arenes ArMen [where ArMen = C6MenH(6-n), and n = 1-6] and FeCl2 in heptane at 90 degrees C in the presence of anhydrous AlCl3 give, for the arenes with n = 1-5, extensive isomerisations and disproportionations involving the methyl groups on the arene rings, and the formation of mixtures of [Fe(ArMen)(2)](2+) dications that defy separation into pure species. GC-MS studies of AlCl3/mesitylene and AlCl3/durene reactions in the absence of FeCl2 (90 degrees C, 2 h) allow quantitative assessments of the rearrangements, and the EINS mechanism (electrophile-induced nucleophilic substitution) is applied to rationalise the phenomena. By contrast, ArMen/FeCl2/AlCl3 reactions in heptane for 24-36 h at room-temperature proceed with no rearrangements, allowing the synthesis of the complete series of pure [Fe(ArMen)](2+) cations in yields of 48-71%.
    Trvalý link: http://hdl.handle.net/11104/0198016