Incorporation of Group 14 Elements into Siloxane-Bridged Paracyclophanes <i>c</i><i>yclo</i>-[<i>p</i>,<i>p</i>‘-Me<sub>2</sub>SiC<sub>6</sub>H<sub>4</sub>EMe<sub>2</sub>C<sub>6</sub>H<sub>4</sub>SiMe<sub>2</sub>O]<sub>2</sub> (E = C, Si, Ge, Sn)<sup>§</sup>
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The bis(arylene silanes) p,p‘-HMe2SiC6H4EMe2C6H4SiMe2H (E = C (10), Si (11), Ge (12), Sn(13)) were prepared by the in situ Grignard reaction of p,p‘-BrC6H4CMe2C6H4Br, Mg turnings, and HSiMe2Cl (for 10) and the Grignard reaction using p-HMe2SiC6H4Br, Mg turnings, and Me2ECl2 (E = Si for 11, Ge for 12, Sn for 13). The oxidation of 10−13 using Pearlman's catalyst, Pd(OH)2/C, in aqueous THF provided the bis(arylene silanols) p,p‘-HOMe2SiC6H4EMe2C6H4SiMe2OH (E = C (14), Si (15), Ge (16), Sn(17)). The HCl-catalyzed condensation of 14−17 in highly diluted solutions of acetone/water afforded the siloxane-bridged paracyclophanes cyclo-[p,p‘-Me2SiC6H4EMe2C6H4SiMe2O]2 (6−9) that incorporate the group 14 elements E = C, Si, Ge, and Sn. Compounds 6−17 were investigated by multinuclear solution and solid-state NMR spectroscopy and 6 and 9 also by X-ray crystallography.
