Basic Research for Establishment of Functionalized Organosilicon Chemistry

(1)多官能团烷基低聚硅烷的区域选择性合成在金属锂的促进下，氨基二氯低聚硅烷与四氢呋喃中的氯硅烷或氯二硅烷发生高选择性的交叉偶联反应，高产率地生成相应的对称和不对称氨基三硅烷。氨基转化为烷氧基或氟。(2)官能化硅烷及其齐聚物的合成以1，1-二氨基硅烷为原料，合成了一系列1，1-二氨基硅烷。合成了硅环连成的低聚(1，1-硅醚)S，作为聚(1，1-硅醚)S的模型化合物.测定了晶体结构和紫外可见光谱，其中叔硅醇和季硅醇在280-290 nm附近有唯一的吸收峰.(3)三[2-(二甲氨基)苯基]硅烷和锗化合物的合成和结构用X射线晶体照相术进行了表征.氢化硅烷和氢化锗中的3个2-(二甲氨基)苯基包裹了键合在硅和锗上的氢原子，导致了短的Si-H键和Ge-H键，增加了键的S特征。硅醇和锗醇通过羟基和氨基之一之间的分子内氢键以单体形式存在。

(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.