Incorporation of group 14 elements into siloxane-bridged paracyclophanes cyclo-[p,p′-Me2SiC6H4EMe2C6H4SiMe2O]2 (E = C, Si, Ge, Sn)

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.