Organopalladium-Functionalized Dendrimers:  Insertion of Palladium(0) into Peripheral Carbon−Iodine Bonds of Carbosilane Dendrimers Derived from Polyols. Crystal Structure of Si{(CH₂)₃O₂CC₆H₄I-4}₄

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Abstract

A carbosilane dendrimer with 12 peripheral iodoarene groups, Si{(CH₂)₃{Si(CH₂)₃O₂C(C₆H₄I-4)}₃}₄ (G₁-ArI, 5), and the corresponding G₀ model compound, Si{(CH₂)₃O₂CC₆H₄I-4}₄ (G₀-ArI, 4) have been prepared from polyol precursors. These compounds react with Pd(dba)₂/tmeda (dba = dibenzylideneacetone, tmeda = N,N,N‘,N‘-tetramethylethylenediamine) to yield periphery-palladated complexes, Si{(CH₂)₃O₂C(C₆H₄-4)PdI(tmeda)}₄ (G₀-ArPdI(tmeda), 6) and Si{(CH₂)₃{Si(CH₂)₃O₂C(C₆H₄-4)PdI(tmeda)}₃}₄ (G₁-ArPdI(tmeda), 7). Dendrimer 7 represents the first example of an exclusively σ-bonded completely periphery-palladated dendrimer. Reactions of the model palladium(II) complexes PdI(EtO₂C(C₆H₄)-4)(tmeda) (2) and PdI(EtO₂C(C₆H₄)-4)(bpy) (3) (bpy = 2,2‘-bipyridyl) with the transmetalation reagents LiMe and SnMe₄ were not successful, while no reaction occurred with the related reagent Sn(CN)Me₃ [CN = 8-(dimethylamino)-1-naphthyl]. The molecular structure of G₀-ArI (5) has been determined by X-ray crystallography and has C_2v symmetry in the solid state.

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This article has been cited by 8 ACS Journal articles (5 most recent appear below).

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  Synthesis of Carbosilane Dendrimers Containing Peripheral (Cyclopentadienyl)(aryloxy)titanium(IV) Units

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• 

  Periphery-Palladated Carbosilane Dendrimers:  Synthesis and Reactivity of Organopalladium(II) and -(IV) Dendritic Complexes. Crystal Structure of [PdMe(C₆H₄(OCH₂Ph)-4)(bpy)] (bpy = 2,2‘-Bipyridine)

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• 

  Suprasupermolecules with Novel Properties:  Metallodendrimers

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• 

  Dendrimers Containing Heteroatoms (Si, P, B, Ge, or Bi)

  Jean-Pierre Majoral and Anne-Marie Caminade
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