Basic Research for Establishment of Functionalized Organosilicon Chemistry

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(1)Regioselective Synthesis of Polyfunctionalized AlkyloligosilanesHighly selective cross-coupling reactions promoted by lithium metal have been achieved between aminodichloromonosilanes and chlorosilanes or chlorodisilanes in THF to form the corresponding symmetrical and unsymmetrical aminotrisilanes in high yields. The amino group is converted to alkoxy group or fluorine.(2)Synthesis of Functionalized Siloles and Silole OligomersA series of 1,1-difunctionalized siloles have been synthesized from 1,1-diaminosiloles. Oligo (1,1-silole)s, silole oligomers catenated through silicons, have been synthesized as model compounds of poly (1,1-silole)s. Crystal structures and UV-vis spectra have been determined, in which tersilole and quatersilole have unique abdorption maxima around 280-290nm.(3)Synthesis and Structures of Tris [2-(dimethylamino) phenyl] silane and -germane CompoundsTris [2-(dimethylamino) phenyl] silane and -germane compounds were synthesized and charcterized by X-ray crastallography. Three 2-(dimethylamino) phenyl groups in the hydrosilane and hydrogermane encapsulate the hydrogen atom bonded to silicon and germanium, which results in the short Si-H and Ge-H bonds and an increase in the s character of the bonds. The silanol and germanol exist as monomers through the intramolecular hydrogen bonding between the hydroxy group and one of the amino groups.