Design of Innovative Ligands and Their Utilization for the Synthesis of Novel Highly Coordinate Organoheteroatom Compounds

1.通过(Z)-1，1，1，6，6，6-hexafluroro-3-iodo-2，5-bis(trifluoromethyl)-3-hexene-2，5-diol与t-BuOCl的氧化环合反应，成功地合成了三配位的1，2-碘氧杂环己烷。X-射线单晶分析表明，该化合物为假三角双锥结构，在顶端有两个氧原子，赤道位置有一个碳原子和两个孤对碳原子，属于T型碘结构。合成了4，4‘，4“-三(叔丁基)-2，2’，2”三甲氧基三苯基甲醇(Ar_3COH)。用三乙基硅烷还原Ar_3COH，然后用n-BuLi锂化合，再与PCl_3反应得到相应的亚膦酸Ar_3Cp(O)HOH。Ar_3Cp(O)HOH与ISI(CH_3)_3的脱甲基化反应成功地合成了具有新型四齿配体的1-氢-5-碳磷杂环己烷。X-射线单晶分析表明，该化合物具有完美的反亲尖结构，氢原子和碳原子位于顶端，三个氧原子位于赤道位置。以1，3，5-三溴-2-碘苯为原料合成了2，2“，6，6”-四甲基-间三苯基-5‘-溴(DenBr)。溴化后与SiCl4反应生成了DEN_4Si，再经DEN_3SiOH和DEN_3SiCl转化为DEN_3SiF。在[2.2.2]络合物存在下，用KF氟化Den_3F，得到相应的五配位二氟硅酸盐K^+、[2.2.2]络合物和Den_3F_2Si^-。本研究项目已成功实现。

1. A tricoordinate 1,2-iodoxetane was successfully synthesized by oxidative cyclization of (Z)-1,1,1,6,6,6-hexafluroro-3-iodo-2,5-bis(trifluoromethyl)-3-hexene-2,5-diol with t-BuOCl. X-ray crystallographic analysis showed that this compound has a pseudo trigonal bipyramidal structure with two oxygen atoms at the apical positions and one carbon atom and two lone pairs at the equatorial positions, which is classified to a T-shaped iodane structure.2. 4,4',4"-tri(t-butyl)-2,2',2" trimethoxytriphenylmethanol (Ar_3COH) was prepared. Reduction of Ar_3COH with triethylsilane, followed by lithiation with n-BuLi and the reaction with PCl_3 gave the corresponding phosphinic acid Ar_3CP(O)HOH after hydrolysis. Demethylation of Ar_3CP(O)HOH with ISi(CH_3)_3 successfully gave the desired 1-hydro-5-carbaphosphatrane with a novel tetradentate ligand. X-ray crystallographic analysis revealed that this compound has perfectly anti-apicophilic structure with hydrogen and carbon atoms at the apical positions and three oxygen atoms at the equatorial positions.3. 2,2",6,6"-Tetramethyl-m-terphenyl-5'-yl bromide (DenBr) was prepared from 1,3,5-tribromo-2-iodobenzene. Lithiation of DenBr followed by the reaction with SiCl_4 gave Den_4Si, which was converted to Den_3SiF via Den_3SiOH and Den_3SiCl. Fluorination of Den_3F with KF in the presence of [2.2.2]cryptand afforded the corresponding pentacoordinate difluorosilicate K^+, [2.2.2]cryptand Den_3F_2Si^-. The present research project has been achieved successfully.