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Reactivity of [Cp′′2Zr(η1:1−E4)] (E=P, As) towards Nucleophiles

Heinl, Veronika ; Seidl, Michael ; Balázs, Gábor ; Scheer, Manfred

Chemistry : a European journal, 2023-06, Vol.29 (34), p.e202301016-n/a [Periódico revisado por pares]

Germany: Wiley Subscription Services, Inc

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  • Título:
    Reactivity of [Cp′′2Zr(η1:1−E4)] (E=P, As) towards Nucleophiles
  • Autor: Heinl, Veronika ; Seidl, Michael ; Balázs, Gábor ; Scheer, Manfred
  • Assuntos: arsenic ; Chemistry ; Condensates ; nucleophile ; Nucleophiles ; Organic phosphorus ; phosphorus ; polypnictogen complexes ; Reagents ; triple decker complex
  • É parte de: Chemistry : a European journal, 2023-06, Vol.29 (34), p.e202301016-n/a
  • Notas: ObjectType-Article-1
    SourceType-Scholarly Journals-1
    ObjectType-Feature-2
    content type line 23
  • Descrição: The functionalization of the polypnictogen ligand complexes [Cp′′2Zr(η1:1‐E4)] (E=P (1 a), As (1 b); Cp′′=1,3‐di‐tertbutyl‐cyclopentadienyl) is focused to modify the features of the polypnictogen unit to explore new synthetic pathways for further transformations. The reaction behavior of 1 towards main group nucleophiles is investigated. The reaction of 1 a with tBuLi leads to the ionic product Li[Cp′′2Zr(η1:1‐P4tBu)] (2) where an organic group is attached to a bridgehead phosphorus atom of the butterfly unit. Further reactions of 2 with quenching electrophilic reagents enable the introduction of other substituents. Moreover, a condensation of 2 to [(Cp′′2Zr)2(μ,η1:1:1:1‐P8tBu2)] (3), containing a novel P8‐unit, has been observed. The reaction of 1 with LiNMe2 and LiCH2SiMe3 leads to a partial fragmentation of the E4 unit and the compounds [Cp′′2Zr(η2‐E3Nu)] (Nu=NMe2: E=P (6 a), As (6 b); Nu=CH2SiMe3: E=P (7 a), As (7 b)) are formed. The reactivity of [Cp′′2Zr(η1:1−E4)] (E=P, As) towards main group nucleophiles is investigated to functionalize the polypnictogen unit. With tBuLi as nucleophile, a single organic group is attached to a bridgehead phosphorus atom. The framework can be extended by further reactions with the quenching reagents [Me3O][BF4] and Ph2PCl. Furthermore, a condensation of two initially formed molecules occurs and a complex bearing a P8 unit is obtained. In contrast, reactions with the nucleophiles LiNMe2 and LiCH2SiMe3 lead to an ion of one pnictogen atom and the formation of a substituted cyclo‐E3 unit on a neutral Cp′′2Zr complex.
  • Editor: Germany: Wiley Subscription Services, Inc
  • Idioma: Inglês
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  • Realização: ABCD-USP USP   Logos de Redes Sociais: Freepik

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