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

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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.