6533b7d6fe1ef96bd1266f55

RESEARCH PRODUCT

Aryldimethylsilyl Modified Hypersilanes

subject

description

Aryldimethylsilyl-substituted hypersilanes ArSiMe2Hyp [Hyp =Si(SiMe3)3; Ar = Mes (3a), Bph (3b), Mph (3c), Pph (3d), Tph (3e); Dpp (3f); with Mes = 2,4,6-Me3C6H2, Bph = 2-PhC6H4, Mph = 2-MesC6H4, Pph = 2′,3′,4′,5′,6′-pentamethylbiphenyl2-yl, Tph = 2′,4′,6′-triisopropylbiphenyl-2-yl and Dpp = 2,6-Ph2C6H3] have been synthesized by a multi-step reaction starting from the readily available starting materials ArI and (thf)xKHyp. For this purpose the aryl iodides were first converted into the lithium aryls by lithium-halogen exchange with n-butyl lithium. A salt-metathesis reaction with SiMe2Cl2 gave the corresponding arylchlorodimethylsilanes (2a–e) in excellent yields. Finally, reaction of 2a–e with (thf)xKHyp afforded the hypersilanes 3a–e in yields up to 86 %. Bis(aryldimethylsilyl)-substituted silanes (ArSiMe2)2Si(SiMe3)2 (Ar = Mph (4c), Tph (4e)) were obtained by the reaction of 3c or 3e with KOtBu and the corresponding chlorosilanes 2c or 2e. All new compounds have been characterized by melting point, elemental analysis, 1H, 13C, and 29Si NMR spectroscopy and for selected species by IR spectroscopy or mass spectrometry. In addition, the solid-state structures of silanes 3a–d, 3f, and 4c have been investigated by single crystal X-ray diffraction.