Carbosilane Dendrimers with End-Grafted Silacrown- and Crown-Ether Units

Abstract

The synthesis of the vinyl-functionalized silacrown ethers 1-methyl-1-vinylsila-8-crown-3 (3) and 1-methyl-1-vinylsila-11-crown-4 (4) by the reaction of (H₂C=CH)MeSi(OEt)₂ (1) with HO(CH₂CH₂O)_nH (2a, n = 2; 2b, n = 3) in presence of catalytic amounts of NaOMe is described. These species can be attached to 1^st and 2^nd generation carbosilane dendrimers by hydrosilylation. Treatment of Si(CH₂CH₂CH₂SiMe₂H)₄ (5) or Si[CH₂CH₂CH₂Si-Me(CH₂CH₂CH₂SiMe₂H)₂]₄ (8) with 3 or 4 produces the respective silacrown ether end-grafted carbosilane dendrimers 6, 7, 9 and 10 in nearly quantitative yield. In a similar manner 2-allyloxymethyl-12-crown-4 (11) gives with 5 and 8 the 12-crown-4 end-capped carbosilane dendrimers 12 and 13, respectively.

The formation of analytical pure and uniform carbosilane dendri­mers with crown ethers at the periphery is based on elemental analysis, IR, ¹H, ¹³C{¹H} and ²⁹Si{¹H} NMR spectroscopy. ESI-TOF MS studies reveal that 7, 10, 12 and 13 form complexes with alkali ions, which enables such species to function as possible ionophores for chemical sensors.

Keywords

carbosilane dendrimers - hydrosilylation - crown ethers - silacrown ethers - chemical sensors

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